Carbohydrate Polymers 124 (2015) 85–89

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Influence of substitution on the rheological properties and gelation of

hydroxyethyl cellulose solution in NaOH–water solvent
Wencong Wang a,b , Faxue Li a , Jianyong Yu c , Patrick Navard b,∗ , Tatiana Budtova b,∗
a
College of Textiles, Donghua University, Shanghai 201620, China
b
MINES ParisTech, PSL Research University, CEMEF – Centre de Mise en Forme des matériaux, CNRS UMR 7635, CS 10207 rue Claude Daunesse,
06904 Sophia Antipolis Cedex, France
c
Modern Textile Institute, Donghua University, Shanghai 200051, China

a r t i c l e i n f o a b s t r a c t

Article history: The rheological properties of hydroxyethyl cellulose (HEC) with a low molar substitution (MS) dissolved
Received 21 December 2014 in 8 wt% NaOH–water were studied as a function of solution temperature, polymer concentration and
Received in revised form 24 January 2015 molar substitution. Special attention was paid to gelation kinetics. Similar to cellulose dissolved in alkali
Accepted 28 January 2015
or ionic liquids, the intrinsic viscosity of HEC decreased with temperature increase, indicating a decrease
Available online 16 February 2015
of solvent thermodynamic quality. The gelation time of HEC solutions decreased exponentially with
temperature but the kinetics is much slower than the gelation of microcrystalline cellulose solutions in
Keywords:
the same solvent. Higher molar substitution leads to slower gelation. The small amount of introduced
Cellulose
Low molar substitution hydroxyethyl groups prevented cellulose aggregation thus increasing solution stability.
NaOH–water solvent © 2015 Elsevier Ltd. All rights reserved.
Intrinsic viscosity
Gelation
Rheology

1. Introduction polymer concentrations higher than the overlap concentration.

It is supposed that cellulose association is driven by hydrogen
To find easy-to-handle and eco-friendly solvents to dissolve bonding. Gelation results in the formation of polymer-rich and
and process cellulose is a “hot” topic attracting a lot of attention polymer-poor domains which leads to micro-phase separation
in academia and industry. 7–9 wt% NaOH–water solutions (with and formation of opaque heterogeneous gels. The use of additives
or without additives such as urea, thiourea, ZnO) could answer delays gelation (Cai & Zhang, 2006; Liu, Budtova, & Navard, 2011),
both requests. The properties of cellulose solutions in these but does not increase the dissolution limit (Egal, Budtova, & Navard,
alkali solvents have been extensively studied during the past two 2008).
decades (Cai & Zhang, 2006; Kamide, Saito, & Kowsaka, 1987; Roy, One of the potential ways in improving cellulose dissolution
Budtova, & Navard, 2003; Zhou, Zhang, & Cai, 2004), and fibers, and stability in alkali solvent and making cellulose II fibers or
films and aerogels were prepared (Cai et al., 2004; Gavillon & films is to perform chemical modifications with low substitution.
Budtova, 2007; Matsui, Sano, Yamane, Kamide, & Okajima, 1995). Hydroxyethyl cellulose (HEC) with low molar substitution (MS)
The main drawbacks of this alkali solvent are the irreversible was synthesized (Wang et al., 2013). HEC fibers were success-
gelation of cellulose solutions with time and temperature (Roy fully spun from 9 wt% solution of this low-substituted etherified
et al., 2003) and a low upper limit of cellulose concentration cellulose with degree of polymerization (DP) 1000 dissolved in
(7–8 wt%) possible to dissolve in this solvent (Egal, Budtova, & NaOH/urea/thiourea = 8/8/6.5 (in wt%) solvent. Solutions were not
Navard, 2007). It was demonstrated that the increase of tempera- gelling within the time needed for spinning (Wang et al., 2013). It
ture leads to the decrease of the thermodynamic quality of 8 wt% was demonstrated that this approach can be an efficient alternative
NaOH–water toward cellulose (Roy et al., 2003). With time and to the viscose process for producing fibers from a non-polluting,
temperature increase cellulose self-aggregates and forms a gel at cheaper and shorter production cycle. However, the addition of
urea or thiourea as stabilizers against gelation imposes extra bur-
dens on the recycling or disposal in the commercial production.
∗ Corresponding author. Tel.: +33 4 93 95 74 70. Pure NaOH–water solvent without any additives is the best choice
E-mail addresses: Patrick.Navard@mines-paristech.fr (P. Navard), to dissolve cellulose because of its cheapness and abundant source
Tatiana.budtova@mines-paristech.fr (T. Budtova). of supply.

http://dx.doi.org/10.1016/j.carbpol.2015.01.065
0144-8617/© 2015 Elsevier Ltd. All rights reserved.
86 W. Wang et al. / Carbohydrate Polymers 124 (2015) 85–89

In this work, we perform a comprehensive study of the influence [η

η], ml/g
of grafted hydroxyethyl groups on the hydrodynamic and viscoelas- HEC-0.20
tic properties of HEC–8% NaOH–water solutions. The goal was to 370 HEC-0.15
understand if and how hydroxyethyl groups affect solution gelation
HEC-0.13
kinetics, which is a critical aspect for process industrialization.
350
2. Experimental

2.1. Materials 330

Cellulose pulp was kindly supplied by Xiangtai Cellulose Corpo-

310
ration (Hubei Province, China); the DP value is 1000 as provided
by the manufacturer. Commercial HEC used in this study was pur-
chased from Sigma–Aldrich. According to the supplier, the DP of 290
this commercial HEC is around 1000, and the MS is about 2.0.
NaOH, acetic acid and ethylene oxide (EO) supplied by Enterprise
Group Chemical Reagent Co., Ltd. were analytical reagents and 270
used without further purification. Silicone oil was purchased from 10 20 30 40 50
Sigma–Aldrich. All chemical reagents were of analytical grade and T, °C
used without further purification. All solutions were prepared with
Fig. 1. Intrinsic viscosity as a function of temperature for three synthesized HEC
distilled water. samples.
The results obtained in this work will be compared with
those published on microcrystalline cellulose (MCC) dissolved in
8–9 wt% NaOH–water (Roy et al., 2003) and in 8 wt% NaOH–0.7 wt% least 15 min before measurement. The initial concentration of HEC
ZnO–water (Liu et al., 2011). The DP of MCC purchased from FMC solution was 2 mg/ml, and five dilutions were made to analyze
Corporation is 230 (Roy et al., 2003) and 170 (Liu et al., 2011). the viscosity–concentration dependence. The mean flow time from
three tests at each concentration was calculated. Temperature was
2.2. Preparation of HEC solutions varied from 20 ◦ C to 40 ◦ C with 5 ◦ C increment. The error in intrinsic
viscosity values was less than 5%.
The synthesis of HEC was conducted in heterogeneous condi-
tions as described in a previous publication (Wang et al., 2013). 2.3.3. Rheological measurements
Briefly, cellulose was dried in vacuum and immersed in 21 wt% The steady and dynamic experiments were performed using
NaOH solution under vigorous stirring for 1 h at ambient tempera- cone-plate geometry (cone angle 2◦ , plate diameter 60 mm) on a
ture. The excess of NaOH solution was removed. Alkaline cellulose Bohlin Gemini rheometer with a Peltier temperature control sys-
was mixed with different amounts of ethylene oxide (EO) and tem. Solutions of different HEC concentrations (4–7 wt%) in 8 wt%
placed under vacuum in a 2 L stainless steel autoclave equipped NaOH–water were studied. Silicone oil (DC 200, Sigma–Aldrich)
with a mechanical stirrer. The mixture was stirred at 40 ◦ C for spread at the edge of gap together with a solvent trap was used
100 min until the pressure inside the autoclave dropped to the to prevent water evaporation. The experimental errors in viscosity
initial value. The as-prepared product was neutralized with acetic and dynamic moduli were less than 10%.
acid, repeatedly rinsed with distilled water, and dried under vac- Steady-state shear flow curves were recorded at shear rates
uum. The mass ratio of EO to cellulose in the reaction medium was between 0.01 and 200 s−1 and at temperature from 20 to 50 ◦ C.
0.13, 0.15 and 0.20, and the corresponding samples are noted as The dynamic rheological measurements were conducted at tem-
HEC-0.13, HEC-0.15 and HEC-0.20. The MS values, as calculated in peratures from 30 to 80 ◦ C with 10 ◦ C increment. The frequency of
Wang et al. (2013), are roughly 0.24, 0.28 and 0.38, respectively. 1 Hz and stress of 0.1 Pa were used and checked to guarantee the
Dry HEC samples were immersed into the 8 wt% NaOH–water solution being in linear viscoelastic regime.
solvent pre-cooled to −6 ◦ C. Transparent solutions with various
HEC concentrations were prepared after mixing at about −6 ◦ C for 3. Results and discussion
2 h. The resultant HEC solutions were subjected to centrifugation at
6000 rpm for 20 min in order to remove air bubbles and then kept in 3.1. Intrinsic viscosity and viscosity–concentration dependence
refrigerator in closed vessels to avoid gelation and oxygen-induced
degradation. Intrinsic viscosity [] was determined using Huggins approach:
 −  
0
2.3. Characterization [] = limC→0 (1)
C0
2.3.1. Solvent density where  and 0 are the solution and solvent viscosity, respec-
The density of 8 wt% NaOH–water solvent was 1.08 g/cm3 , which tively, and C is polymer concentration. The intrinsic viscosity of
was determined by measuring the weight of solution in a given HEC solution as a function of temperature is presented in Fig. 1.
volume of 100 ml at 20 ◦ C. Solution concentration is given in wt% for At a given temperature, the values for all three solutions are
most of the rheological studies and in g/ml for the part concerning very similar within the experimental errors; the intrinsic viscos-
the determination of the intrinsic viscosity. ity of HEC-0.20 is slightly higher probably because the increasing
amount of hydroxyethyl groups increases chain rigidity due to
2.3.2. Intrinsic viscosity measurements steric hindrance. For all samples, the intrinsic viscosity decreases
Intrinsic viscosities of HEC–8 wt% NaOH–water solutions were with the increasing temperature: this phenomenon had already
measured with a Lauda PVS-1 (Lauda, Germany) Ubbelohde type been reported for non-modified MCC in 8 wt% NaOH–water with
viscometer with capillary tube 53110/I (Schott AG, Germany). The and without additives (Liu et al., 2011; Roy et al., 2003) and also for
viscometer was placed in a thermally controlled water bath at cellulose and for cellulose acetate in 1-ethyl-3-methylimidazolium
 W. Wang et al. / Carbohydrate Polymers 124 (2015) 85–89 87

η, Pa s
100
7%

6%

5%

10 4%

1
0.01 0.1 1 10 100 1000
shear rate, 1/s

Fig. 2. Viscosity versus shear rate for HEC-0.13 solutions of 4, 5, 6 and 7 wt% at 20 ◦ C.
Fig. 3. Viscosity versus HEC-0.13 concentration for 20 and 40 ◦ C. Solid lines are linear
(low concentration) and power-law (higher concentrations, Eq. (2)) approximations.
acetate (EmimAc) ionic liquid (Gericke, Schlufter, Liebert, Heinze, Inset: master plot for HEC-0.13 for 20, 30 and 40 ◦ C.
& Budtova, 2009; Rudaz & Budtova, 2013). Huggins constants for
all HEC samples varied from 0.53 to 0.65; no trend as a function
of temperature or molar substitution could be observed. The val-
region), which correlates well with the values found via intrinsic
ues obtained indicate that 8% NaOH is a theta with a slight trend
viscosity.
to good solvent for low-substituted HEC. Temperature increase
Relative viscosity is used for excluding the influence of tem-
decreases the thermodynamic quality of most of cellulose solvents,
perature on solvent. The profiles of relative viscosities at three
and the presence of grafted hydroxyethyl groups does not change
temperatures of 20, 30 and 40 ◦ C against polymer concentration
this trend.
perfectly fall on one master plot as shown in the inset of Fig. 3.
The overlap concentration was calculated as the inverse intrin-
The viscosity decreases with the increase of temperature as
sic viscosity. It varies from 0.0028 to 0.0032 g/ml (equivalent to
shown in Fig. 3 for the temperature interval of 20–40 ◦ C. The influ-
0.26–0.3 wt%, respectively), which is lower than that obtained for
ence of temperature on the properties of HEC solutions has to
MCC dissolved in 8 wt% NaOH–water or in 0.7 wt% ZnO–8 wt%
be taken with care: as it will be shown below, above the over-
NaOH–water (around 1 wt%) (Liu et al., 2011; Roy et al., 2003) due
lap concentration, solutions in semi-dilute state are gelling with
to the higher molecular weight of cellulose used in this study.
time and/or temperature increase. To apply the classical analysis
An example of the steady-state shear flow curves for HEC-0.13
of viscosity-temperature dependence (Arrhenius approach), only
solutions with various concentrations is shown in Fig. 2. Similar
rather low temperatures (here, below 40 ◦ C) can be used. The acti-
results were acquired for the other two HEC samples. A Newtonian
vation energy Ea was determined according to Eq. (3).
plateau is seen at low shear rates. The increase of shear rates leads
to shear thinning which occurred at lower shear with the increase E 
a
of solution concentration.  = A × exp (3)
RT
Fig. 3 shows viscosity of HEC-0.13 solutions in 8 wt% NaOH sol-
vent as a function of solution concentration at two temperatures. where  is viscosity mean value in the Newtonian region, A is a con-
Data were collected from two sets of measurements: at low solu- stant, and T is the absolute temperature of the HEC solutions. The
tion concentrations, viscosity was taken from the measurements activation energy for HEC solutions varies from 27 to 33 kJ/mol for
in Ubbelohde viscometer, and in the semi-dilute region the mean the concentrations studied, which is located in the range of values
value of viscosity in Newtonian region was calculated from the obtained for cellulose in the same solvent (Egal, 2006).
steady state experiments. We checked that for solutions in dilute
region with the viscometer used and at flow times obtained the
flow was Newtonian for the shear rates developed in the capil- 3.2. Gelation of HEC solutions
lary. The values from two different techniques match very well by
allowing the analysis of the whole viscosity-concentration depend- Similar with MCC solutions in 7–9 wt% NaOH–water, HEC–8 wt%
ence and building a master plot of relative viscosity /0 versus NaOH–water solutions are gelling with time at a given tempera-
concentration (see inset of Fig. 3). A linear dependence of vis- ture and with temperature increase. An example of the evolution
cosity on concentration was recorded for polymer solutions with of elastic (G ) and viscous (G ) moduli of 6 wt% HEC-0.13 solu-
low concentrations, as expected. At high concentrations power-law tions as a function of time at two temperatures, 60 and 70 ◦ C, is
dependence was observed with n being around 3.7–3.8: shown in Fig. 4. At short times, G is lower than G indicating that
HEC–0.13–8 wt% NaOH are visco-elastic solutions. With time, G
∼C n (2)
increases and overpasses G : solution is reaching a gel point. In the
Similar results were found for cellulose–EmimAc solutions (n = 4 first approximation, we can determine gelation time as the moment
below 40 ◦ C) and cellulose–LiCl–DMAc solutions (n = 3 for bacterial when G = G = Ggel .
cellulose and n = 4 for cotton linters) (Gericke et al., 2009). The over- The modulus at the gel point Ggel of HEC–0.13–8 wt%
lap concentration obtained from the turning point of the viscosity NaOH–water as a function of polymer concentration at various tem-
versus concentration curve in Fig. 3 is around 0.3 wt% (end of linear peratures is shown in Fig. 5. Higher HEC concentration, higher the
88 W. Wang et al. / Carbohydrate Polymers 124 (2015) 85–89

G', G'', Pa tgel, min 4%

10000
120 5%
G', 60°C
6%
100 G', 70°C
1000
7%
MCC 4%
80
MCC 6%

60 G'', 60°C 100

40
G'', 70°C 10
20

0
1
0 20 40 60 80 100
0 20 40 60 80 100
time, min
T, °C
Fig. 4. Time dependence of G and G of 6 wt% HEC-0.13 8 wt% NaOH aqueous
solution at 60 and 70 ◦ C. The corresponding gelation times are shown with arrows. Fig. 6. Gelation time of HEC-0.13 (this study) and of MCC solutions (Liu et al., 2011)
with various concentrations as a function of temperature. Solid lines are approxi-
mations according to Eq. (5).
modulus, as expected; the trend can be described with a power law
similar to Eq. (2) for viscosity–concentration dependence:
Gelation time tgel as a function of temperature is presented in
Ggel ∼C m (4) Fig. 6 for HEC-0.13 solutions with various concentrations together
with data for MCC dissolved in 8% NaOH–water taken from previous
For HEC-0.13 solutions, the exponent m varies from 3.4 for 30 ◦ C
study (Liu et al., 2011). It was shown that gelation time of MCC–8%
to 4.6 for 70 ◦ C. Similar values were obtained for gelling MCC–8 wt%
NaOH solutions is exponentially proportional to temperature (T)
NaOH–water solutions (Gavillon & Budtova, 2007). Similar scaling
(Gavillon & Budtova, 2007; Liu et al., 2011; Roy et al., 2003):
exponent, close to 3, was reported for gelling methylcellulose aque-
ous solutions (Sarkar, 1995; Li, 2002) and around 3.6–4.4 for gelling tgel ∼A × exp(−aT ) (5)
hydroxypropylmethyl cellulose (Sarkar, 1995). Gelation of cellulose
is accompanied by chains aggregation and microphase separation where “A” and “a” are adjustable constants characteristic for each
which can be the reason of strong concentration dependence. solution. In the case of cellulose grafted with hydroxyethyl groups,
Fig. 5 also shows that the Ggel decreases with the increasing the gelation time also exponentially decreases with temperature,
temperature. A similar trend has been reported in the rheological but the rate of gelation is very different: the slope of the fitting line
study of MCC–NaOH solutions (Roy et al., 2003). Chain mobility, for tgel versus temperature is much steeper for MCC solutions than
which increases with temperature, may counterbalance interac- that for HEC solutions (Fig. 6). For HEC-0.13 solution, the exponent
tions between HEC chains resulting in the formation of weaker “a” value varies from 0.084 to 0.096 for concentrations from 4 to
gels. 7 wt% which is three to four times lower than the values obtained
for the MCC solution, a = 0.3–0.4 (Gavillon & Budtova, 2007; Liu
et al., 2011; Roy et al., 2003). The gelation times at a given tempera-
1000 ture of HEC solutions are much longer as compared to MCC solution
Ggel, Pa
as demonstrated in Figure 6, although the MCC has lower DP. For
example, at 30 ◦ C, a 4 wt% solution of MCC in 8% NaOH–water is
gelling in 7 min while a 4 wt% HEC-0.13 solution in 8% NaOH–water
30°C is gelling in 43 h. Grafted hydroxyethyl groups increase the distance
100 between macromolecules and decrease their interactions, which
50°C seems to prevent cellulose aggregation and thus delay the gelation.
The influence of grafted groups on the gelation of HEC solu-
60°C tions is demonstrated in Fig. 7 which shows the gelation time as
a function of temperature for three HEC solutions of the same con-
70°C
centration (6 wt%). The exponent in Eq. (5) is identical for three
10
solutions but the constant “A” decreases with the decrease of the
amount of grafted groups. It takes a longer time to gel HEC-0.20
solution than HEC-0.13 or HEC-0.15 solution. A 6 wt% commercial
HEC dissolved in 8 wt% NaOH–water is gelling in 8 h at 60 ◦ C. In
other words, higher the molar substitution is, slower the gelation
1 is. The increase of the number of grafted hydroxyethyl groups pre-
1 10 vents the formation of hydrogen bonds between cellulose chains
CHEC-0.13, wt% and thus aggregation/gelation becomes more difficult.
The gelation time is shorter with the increased polymer concen-
Fig. 5. Modulus at gel point (G = G ) of HEC-0.13 as a function of polymer concen-
tration at various temperatures. Lines are power-law approximations according to tration as demonstrated in Fig. 8 for the inverse of tgel as a function
Eq. (4). of HEC-0.13 solution concentration at various temperatures. It
 W. Wang et al. / Carbohydrate Polymers 124 (2015) 85–89 89

10000 tgel, min 4. Conclusions

Hydrodynamic properties and gelation of hydroxyethyl cellu-

y = 41370e-0.092x lose with low molar substitution dissolved in 8 wt% NaOH–water
(HEC-0.20)
were studied as a function of the molar substitution, polymer con-
centration and solution temperature. Intrinsic viscosity decreases
1000 HEC-0.20 with temperature increase similar to what was already reported for
cellulose dissolved in the same solvent or in ionic liquid and also
HEC-0.15 cellulose derivatives dissolved in various solvents.
y = 28728e-0.093x
HEC–8 wt% NaOH–water solutions are gelling with time and
(HEC-0.15) HEC-0.13 temperature, similar to MCC solutions in alkali solvent. However,
gelation kinetics of HEC solutions is much slower as compared to
100 non-modified cellulose: higher is the degree of molar substitution,
slower the gelation is. Grafted hydroxyethyl groups decrease the
y = 24487e-0.093x
probability of formation of hydrogen bonds and prevent cellulose
(HEC-0.13)
aggregation due to sterical hindrance; weak substitution can be a
way of stabilization of cellulose–NaOH solutions. The increase of
10 stability gives the HEC with low substitution more potential in the
0 20 40 60 80 100 fiber manufacture.
T, °C
Acknowledgment
Fig. 7. Comparison of gelation times as a function of temperature for three samples
at 6 wt% concentration: HEC-0.13, HEC-0.15 and HEC-0.20. Lines are approximations
Authors acknowledge the financial support of Fundamental
according to Eq. (5).
Research Funds for the Central Universities, China.

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