Food Hydrocolloids 58 (2016) 235e245

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Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Flow behaviours of cellulose and carboxymethyl cellulose from

grapefruit peel
Mukaddes Karataş, Nurhan Arslan*

, Turkey
Faculty of Engineering, Department of Chemical Engineering, Fırat University, 23279 Elazıg

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

Article history: The viscosity of cellulose from defatted, protein, pectin and hemicellulose free, delignified grapefruit peel
Received 14 November 2015 was measured at different temperatures (10e60
C) and concentrations (1e10 kg/m3) with a capillary
Received in revised form flow technique. The effects of concentration and temperature on the viscosity of cellulose were examined
19 February 2016
by utilizing sixteen derived models describing the combined effects of temperature and concentration on
Accepted 28 February 2016
the viscosity. The constants of models fitted to the experimental data were predicted by nonlinear
Available online 3 March 2016
regression analysis. The grapefruit peel cellulose was converted carboxymethyl cellulose (CMC) by
etherification using sodium monochloroacetate and sodium hydroxide. The apparent viscosities of CMC
Keywords:
Grapefruit peel
from grapefruit peel cellulose were measured by using a rotational viscometer at concentrations varied
Cellulose from 15 kg/m3 to 35 kg/m3 for temperatures 10e60
C. Apparent viscosity decreased with increasing
Carboxymethyl cellulose shear rate. Apparent viscosity increased with an increase in concentrations for all temperatures and
Flow behaviour decreased with the temperature at which viscosity was measured. The Arrhenius equation was used to
describe the temperature dependence of viscosity. The power law, Bingham and Casson models were
Chemical compounds studied in this article:
used for description of flow. The power model given a good fit for the experimental data of CMC at
Cellulose (PubChem CID: 24748)
Carboxymethyl cellulose (PubChem CID:
different temperatures and concentrations. The consistency coefficient and flow behaviour index were
6328154) calculated by using the power-law model. The CMC solutions were found to exhibit pseudoplastic and
Chloroform (PubChem CID: 6212) thixotropic flow behaviours. At various stages of cellulose and CMC production that concentrations and
Methanol (PubChem CID: 887) temperatures changed, the best model among derived models may be used to estimate the viscosity of
Ammonium oxalate (PubChem CID: 14213) cellulose and CMC from grapefruit peel in the range of temperatures and concentrations studied.
Sodium hydroxide (PubChem CID: 14718) © 2016 Elsevier Ltd. All rights reserved.
Chloroacetic acid sodium salt (PubChem
CID: 23665759)
Isobutyl alcohol (PubChem CID
6560)
Acetic acid (PubChem CID: 176)
Hydrochloric acid (PubChem CID: 313)

1. Introduction chemically reactive and strongly hydrophilic (Benyounes &

Cellulose is a linear polymer of b-(1 / 4)-D-glucopyranose units
in 4C1 conformation. Cellulose is the most abundant natural,
renewable, biodegradable polymer. It constitutes about 33% of all
plants' matter. Cellulose found in plants as microfibrils is the most
important structural component of plant cell walls (Kirk & Othmer,
1967). There are potential sources of cellulose such as orange peel,
palm kernel and pomelo peel (Bicu & Mustata, 2013; Chumee &
Seeburin, 2014; Yan, Krishniah, Rajin, & Bono, 2009). The pres-
ence of polar carboxyl groups makes the cellulose soluble,
* Corresponding author.
E-mail address: narslan2@firat.edu.tr (N. Arslan).
Benmounah, 2012). Sodium carboxymethyl cellulose (CMC) is a
water soluble negatively charged polysaccharide. CMC resulting
from the interaction of salts of chloroacetic acid with alkali cellu-
lose is the most widely used cellulose ether, with applications in
the food, oil exploration, detergent, paper, textile, pharmaceutical
and paint industries as thickener or a flocculating agent (Haleem,
Arshad, Shahid, & Tahir, 2014; Chumee & Seeburin, 2014;
Melander & Vuorinen, 2001; Oun & Rhim, 2015; Taubner,
Synytsya, & Copikova, 2015). Many researchers have studied the
production of CMC from agricultural waste cellulose sources such
as sugar beet pulp (Tog
rul & Arslan, 2003, 2004), cashew tree gum
(Silva et al., 2004), Cavendish banana pseudo stem (Adinugraha,
Marseno, & Haryadi, 2005), sago waste (Pushpamalar, Langford,
Ahmad., & Lim, 2006), palm kernel cake (Bono et al., 2009),

http://dx.doi.org/10.1016/j.foodhyd.2016.02.035
0268-005X/© 2016 Elsevier Ltd. All rights reserved.
236 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245
durian rind (Rachtanapun, Luangkamin, Tanprasert, & Suriyatem,
2012), pomelo peel (Chumee & Seeburin, 2014), cotton gin waste
(Haleem et al., 2014), cotton linter pulp (Oun & Rhim, 2015) and
office waste paper (Joshi et al., 2015), However, to date, to the best
of our knowledge, no systematic work has been reported on the
isolation of cellulose from grapefruit peel and then the carbox-
ymethylation of isolated cellulose to CMC. CMC is the most widely
used cellulose derivative, which composed of b-D-glucose and b-D-
glucopyranosyl-2-O-(carboxymethyl)-monosodium salt connected
via b-(1,4-glycosidic) bonds (Rachtanapun et al., 2012). Anhydrous
glucopyranose unit enables some emulsifying or stabilizing func-
tions, in addition to its thickening capacity, thermo-plasticity sur-
face activity, film forming ability and suspending and stabilising
characteristics. CMC at different concentrations can be used to in-
crease viscosity, stabilise suspension or emulsions and maintain
flow characteristics of foods (Bekkour, Sun-Waterhouse, &
Wadhwa, 2014). CMC is abundantly available biopolymer with non-
toxic, biodegradable, biocompatible, and good film forming prop-
erties (Almasi, Ghanbarzadeh, & Entezami, 2010).
The viscosity of cellulose needs to be known to provide primary
importance to the cellulose industry. The accurate viscosity data for
cellulose solutions over wide temperature and concentration re-
gions are needed for several engineering applications in the cel-
lulose production industry. Both the temperature and
concentration variations of the viscosity of fluids were combined by
several investigators in a single equation (Magerramov,
Abdulagatov, Azizov, & Abdulagatov, 2007). To our knowledge, no
previous work on the rheological properties of cellulose from
grapefruit peel has been reported.
The flow curves of fluid are modelled by using the several
models such as Newtonian, Bingham, power law, Casson and
Herschel-Bulkley which are the most frequently used for engi-
neering applications (Cancela, Alvarez, & Maceiras, 2005; Hojjat,
Etemad, Bagheri, & Thibault, 2011; Singh & Sharma, 2013; Sopade
& Kiaka, 2001; Steffe, 1992; Zhong, Oostrom, Truex, Vermeul, &
Szecsody, 2013). The rheological properties of CMC depend on the
concentration of CMC solutions and the degree of substitution
(Barba, Montane , Farriol, Desbrie
res, & Rinaudo, 2002). Since
experimental viscosity data in production process of CMC from
grapefruit peel cellulose are needed to make engineering calcula-
tions on heat-transfer coefficients, evaporation performance,
pumping and pipe requirements, mixing requirements and equip-
ment design, viscosity must be correlated with temperature and
concentration. Viscosity data on the rheological behaviour of CMC
from various sources have been reviewed by Cancela et al. (2005),
Dapia, Tovar, Santos, and Parajo (2005); Edali, Esmail, and
Vatistas (2001); Ghannam and Esmail, (1997), Kelessidis,
Poulakakis, and Chatzistamou (2011) Lin and Ko (1995), Lindberg,
€ , and Martinmaa (1987) and Pilizota, Subaric and Lovric
Sirvio
(1996), but no published information is available on the rheolog-
ical behaviour of CMC from grapefruit peel.
The main objectives of the present study were: (1) to isolate the
cellulose from grapefruit peel, (2) to develop the equations for
correlation of the experimental viscosity data of grapefruit peel
cellulose solutions as a function of temperature and concentration,
(3) to synthesize CMC from grapefruit peel cellulose, (4) to inves-
tigate the rheological behaviours of CMC solutions at several tem-
peratures, concentrations and shear rates, and (5) to discuss the
behaviour of the temperature and concentration dependences of
apparent viscosities of CMC from grapefruit peel in light of the
various theoretical models describing the combined effect of tem-
perature and concentration.
2. Materials and methods
2.1. Chemical analysis of grapefruit
Grapefruit peel was analysed for protein and ash (AOAC, 1984).
Fat content was measured by the Soxhlet method using petroleum
ether. Polysaccharide was determined by difference. All results
were calculated on an oven-dry matter basis. All analysis were
performed in duplicate and the mean values were reported.
2.2. Isolation of cellulose from grapefruit peel
Albedo and flavedo were obtained from grapefruit peels.
Grapefruits were purchased from the open market. Grapefruit peels
were segmented to a particle size of about 1 cm  1 cm, air-dried,
and ground in a laboratory milling machine to pass a 50-mesh size
screen. The ground pulp was heated to 97
C in a water bath for
about 10 min to inactivate pectic enzymes. Then, it was washed
with water, filtered through a suction filter, dried at 50
C and
sieved. A 50-mesh fraction was used in experiments. The fat from
dried and ground grapefruit peel (7 g) was removed by using
conventional soxhlet extractor with chloroform:methanol (2:1, v/v)
for 6 h. The defatted grapefruit peel was mixed with 0.1 M Na3PO4
(350 ml) to bring it to pH 7.5. Proteolysis was performed by the
addition of protease (35 mg). After incubation overnight at 37
C,
the sample was filtered. The deproteinated grapefruit peel was
mixed with 750 ml of 0.25% ammonium oxalate (w/v) (pH:3.5). The
mixture was shaken at 75
C in water bath for 60 min and filtered.
10% NaOH (1 g residue/20 ml NaOH) was added the depectinated
grapefruit peel. The mixture was shaken at 35
C in water bath for
22 h, filtered and washed distilled water to remove the base. The
hemicellulose-free grapefruit peel was mixed with 100 ml of
distilled water, 5 ml of 10% acetic acid and 2 g NaCl. The mixture
was shaken at 75
C in water bath for 60 min and filtered. The
residue was washed with distilled water and ethanol to remove
acid, and then dried at 50
C in an oven for 16 h (Kirk & Othmer,
1967).
2.3. Conversion of isolated cellulose into CMC
The carboxymetylation of cellulose is a two step process and is
accompanied by a undesired side reaction (Rajput, Pandey, & Joshi,
2015). The first step is activation of cellulose with an aqueous NaOH
in the slurry of an organic solvent. The second step is reaction of
cellulose with Na salt of chloroacetic acid. The main reaction
comprises of
Cell-OH þ NaOH / RcellOH$NaOH
Cell-OH$NaOH þ ClCH2COONa / Cell-O-CH2COONa þ NaCl þ H2O
The side reaction results in the formation of sodium glycolates
from NaOH and sodium monochloroacetate.
NaOH þ ClCH2COONa / HOeCH2COONa þ NaCl
Isolated cellulose from grapefruit peel was converted to CMC in
two steps: alkalization and etherification of cellulose. Carbox-
ymethylation of the cellulose from grapefruit peel was performed
as follows: Dried cellulose was ground to pass a 50-mesh size
screen. Dried and ground cellulose (2 g) was dispersed in isobutyl
alcohol (100 ml) containing NaOH of 30% (20 ml) at room tem-
perature with continuous stirring for 90 min. The cellulose-NaOH
activation reaction is generally performed at room temperature.
The mixture was filtered to a weight of about 6.4 g and shredded for
 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245
90 min in a shredder. The sodium chloroacetate (3 g) was added
and stirred at 70
C for 6 h. The temperature was controlled within
±0.1
C using a circulating wash bath during carboxymethylation.
The reaction product was neutralized using dilute glacial acetic
acid. The mixture was then filtered and the residue was suspended
in 70% methanol to remove undesired salts, filtered. The residue
from the filtration was dried at 70
C overnight and the powder
obtained was CMC (Kirk & Othmer, 1967). The degree of substitu-
tion (DS) of CMC was determined by potentiometric titration, the
standard method (Jiang et al., 2011).
2.4. Rheological measurements
The strong mineral acids dissolve cellulose in certain concen-
tration ranges. This may be presumed to be due to the formation of
the eOHþ 2 ion attached to the cellulose (Ott, 1946). Cellulose solu-
tions were prepared by mixing the required amount of cellulose to
produce cellulose solutions of the intended concentration (1, 2, 4, 6,
8 and 10 kg/m3) in HCl solution of 37%. Solutions were mechanically
mixed to solubilize the cellulose and to disrupt any weakly floc-
culated aggregates prior to any measurements. Because diluted
organic solutions are generally Newtonian in character, it has been
assumed that the cellulose solutions studied were Newtonian (Kirk
& Othmer, 1970).
An Ubbelohde type capillary viscosimeter (capillary no: II,
ID:1.13 mm) was immersed to water in glass cylindrical vessel
connected to a thermostated heat bath circulator which can be
adjusted to give the desired temperature. The temperature was
maintained as desired with an accuracy of ±0.1
C. Flow times were
recorded with a stopwatch with reproducibility ±0.2 s. The vis-
cosity of cellulose solutions of different concentrations was calcu-
lated by means of flow times at 10
C intervals from 10
C to 60
C.
CMC solutions were prepared by hydrating in distilled water the
CMC from grapefruit peel for overnight. Before rheological mea-
surements, solutions were mixed vigorously with a magnetic stirrer
for 24 h to release air bubbles.
To characterize the rheological properties, studies were carried
out by rotational rheometry. The torque was measured by using a
Brookfield viscometer (LVDV-E model; Brookfield Engineering
Laboratories. Inc., Stoughton, MA, USA) with various spindle
speeds (6, 10, 12, 20, 30, 50 and 60 rpm). A rotational steady shear
flow measurement from shear rate of 1.32 s1 to shear rate of
13.2 s1 was performed. Spindle LV-1 was used to get readings
within the scale. The rheological properties of CMC solutions
were evaluated at different concentrations, ranging between 15
and 35 kg/m3 and at different temperatures (10, 20, 30, 40, 50 and
60
C). A 200-ml cylindrical vessel was used for all the mea-
surements and sample was added to cover the immersion grooves
on the spindle shafts. For each test, approximately 150 ml of
sample was filled into the cylindrical vessel and allowed to
equilibrate at desired temperature. In order to control the tem-
perature, the water-jacketed stainless steel cylindrical vessel was
connected to a constant temperature bath which was able to
maintain temperature uniformity within ±0.1
C. The shear rate
was increased continuously from 1.32 to 13.2 s1 giving seven
readings. The torque readings were taken after 60 s in each
sample, with a resting in time between the measurements at the
different spindle speeds. CMC solutions were sheared at spindle
speed of 30 rpm until an equilibrium state was reached to
examine the change in the apparent viscosity with shearing time.
All rheological tests were replicated two times in order to
investigate the reproducibility of the results. The reproducibility
was ±5% on an average.
Shear rates for CMC solutions were calculated by using the cy-
lindrical spindle factors given by Brookfield (Brookfield
237
Engineering Labs. Inc., Stoughton, MA, USA) for spindle LV-1.


dVf dr ¼ 0:22N (1)
where dVf/dr (s1) is the shear rate, N is the spindle speed (rpm).
To calibrate the viscometer, Brookfield silicone viscosity stan-
dard (nominal viscosity at 25
C: 1000 mPa s) was used. The
following equation was used to calculate spindle calibration factor
for any spindle speed.
f ¼ R=100 (2)
where f is the spindle calibration factor, R is the full scale viscosity
range.
Apparent viscosity values (ha) were calibrated using the
following equation.
ha ¼ f ð% TorkÞ (3)
Shear stress was found by the following relation.


trf ¼ ha dVf dr (4)
where trf is the shear stress (mPa),ha is the apparent viscosity
(mPas), dVf/dr is the shear rate (s1), Vf is the velocity in direction
along the axis of rotation, r is the radial distance.
2.5. Statistical analysis
The Statistical software package (Statistica for Windows 5.0,
1995) was used to carry out the nonlinear regression analysis of
experimental viscosity data for both cellulose and CMC. The anal-
ysis of variance (ANOVA) was used to evaluate statistically the ef-
fect of concentration on the flow activation energy and the
consistency index.
3. Results and discussion
The composition of dried grapefruit peel was 3.86% ash, 6.23%
crude protein, 2.25% crude fat (on a dry weight basis). Poly-
saccharide content calculated by difference was 87.66%. The yield
percentage of cellulose production from dried grapefruit peel was
found to be 20.04%. The degree of substitution (DS) of CMC is
defined as the average number of carboxymethyl groups per
repeating unit and is usually in the range of 0.4e1.5. CMC generally
exists under the sodium salt form, a water-soluble product for
DS > 0.5. A maximum degree of substitution of 1.5 is permitted, but
more typically DS is in the range 0.60e0.95 for food applications
(Schmitt, Sanchez, Desobry-Banon, & Hardy, 1998). The degree of
CMC solubility depends on substitution of a carboxymethyl group
instead of the hydroxyl groups in cellulose structure. The degree of
substitution of CMC from grapefruit peel was found to be
0.798 ± 0.014 (average ± standard deviation of three replicate
trials).
3.1. The combined effect of temperature and concentration on
viscosity of cellulose
The effect of concentration and temperature on the viscosity of
cellulose solutions of 1, 2, 4, 6, 8 and 10 kg/m3 is given in Fig. 1.
The cellulose viscosity decreased as the temperature at which
the viscosities were measured increased and viscosity increased at
higher concentrations (Fig. 1). Decrease in viscosity is due to the
interactions of the molecules in solution, which are weaker at
higher temperature. This effect is caused by the loss of hydradation
water around the polymer molecule (Casas, Mohedano, & Ochoa,
238 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245
Fig. 1. Effect of concentration and temperature on viscosity of cellulose solutions
▵ ▫
(temperature (
C): 10, :20, 30, -40, B50, C60).
2000). It was stated that dilute cellulose-NaOH complex solutions
experienced a quite different rheological behaviour from those at
higher concentrations and a Newtonian plateau was observed with
decreasing cellulose concentration (Zhang, Li, & Yu, 2011).
To point out the exponential dependence of fluid viscosity and
temperature, the following linearized Arrhenius equation was used
(Grigelmo, Ibarz, & Martin, 1999). The model is based on the
assumption that the fluid flows obeys the Arrhenius equation for
molecular kinetics.
ln h ¼ ln ho þ Ea =RT (5)
The values of the flow activation energies were calculated from
the linear plot of ln h versus 1/T in Eq. (4) for the measured vis-
cosities of cellulose as a function of concentration. The intercepts
and slopes of the linear plot are flow activation energy and
parameter ln hο, respectively. The values of the parameter hο and
the flow activation energy for cellulose from grapefruit peel were
found to be 31.72  10336.40  103 mPas and 9.56e10.54 kJ/
mol, respectively (Table 1). It were found that the values of the
parameter hο and the flow activation energy for cellulose from
orange peel were 48.37  10351.39  103 mPas and
8.87e9.05 kJ/mol, respectively (Yaşar, Tog
rul, & Arslan, 2007). As
seen from Table 1, the flow activation energy increased with
increasing concentration and the parameter hο decreased with an
increase in concentration. Flow activation energy is a measure of
viscosity sensitivity to temperature changes. Therefore, the cellu-
lose solution at concentration of 10 kg/m3 is more sensitive to
temperature in comparison with the cellulose solutions at other
concentrations. As a result of the analysis of variance (ANOVA), it
was revealed that the increasing concentration had insignificant
effects on the activation energies (p > 0.05). The parameter hο
Table 1
The values of the parameter hο and the flow activation energy for cellulose from
grapefruit peel.
C (kg/m3) ho  103(mPa s) Ea (kJ/mol) r2
1 36.40 9.56 0.9918
2 35.54 9.86 0.9909
4 35.42 9.96 0.9950
6 34.64 10.09 0.9999
8 33.32 10.33 0.9982
10 31.72 10.54 0.9992
descended for a higher concentration since the changes in viscosity
at high concentrations was more than those at low concentrations
for all temperatures.
Temperature has an important influence on the flow behaviours
of solutions. The effect of temperature on viscosity is generally
expressed by Arrhenius and Andrade equations. The effect of
temperature on the viscosity of cellulose solutions was determined
by using Andrade equations (Constella, Lozano, & Crapiste, 1989;
Speers & Tung, 1986):
ln h ¼ A þ ðB=TÞ þ DT (6)
log h ¼ ðA=TÞ  B (7)
h ¼ A  BlogT (8)
where h is the viscosity of cellulose solution (mPa s), ho is a pre-
exponential factor (mPa s), Ea is the activation energy of flow (kJ/
mol), R is the universal gas constant (8.314  103 kJ/mol K), T is the
absolute temperature (K) and A, B, D are constants.
The effect of concentration on the viscosity is generally
described by either an exponential or a power-law relationship
(Speers & Tung, 1986).
h ¼ K1 ðCÞA1 (9)
h ¼ K2 expðA2 CÞ (10)
where K1 (mPa s ðkg=m3ÞA1 ), K2 (mPa s), A1 (dimensionless) and
A2 (kg/m3)1 are constants and C is the concentration of cellulose
solutions (kg/m3).
Similarly, relationships between A, B, D constants in Eqs. (6)e(8)
and concentration can be written in of forms of Eqs. (11) and (16).
A ¼ K3 ðCÞA3 (11)
A ¼ K4 exp ðA4 CÞ (12)
B ¼ K5 ðCÞA5 (13)
B ¼ K6 exp ðA6 CÞ (14)
D ¼ K7 ðCÞA7 (15)
D ¼ K8 exp ðA8 CÞ (16)
The effect of temperature and concentration on viscosity could
be combined into a single equation for use in applications where
simultaneous heat and mass transfer takes place. Sixteen different
theoretical models (eight different models by combining the Eq. (6)
and Eqs. 11e16, four different models by combining the Eq. (7) and
Eqs. 11e14, four different models by combining the Eq. (8) and Eqs.
11e14) were derived. In these models, the viscosity was related to
temperature and concentration. Sixteen different theoretical
models describing the temperature and concentration dependence
of cellulose viscosity were applied to the experimental data to
determine the best fit for the temperature range 10e60
C and the
concentration range 1e10 kg/m3. The constants in models were
determined by the nonlinear regression analysis to examine the
goodness-of-fit of the models. Statistical software package
(Statistica for Windows 5.0, 1995) was used to perform the
nonlinear regression analysis of experimental viscosity data. The
quality of the fit of the model was estimated using the various
 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245 239

statistical parameters such as root mean square error (RMSE), chi- Table 3
square c2, mean bias error (MBE), mean percentage error (MPE) Statistical test results of models derived for cellulose.

and the coefficient of determination r2. These parameters can be Model RMSE c2 MBE MPE r2
calculated as follows: 1 0.030930 0.001148 0.000334 0.026067 0.9948
2 0.037197 0.001660 0.001065 0.147791 0.9924
" #1 2
=
3 0.042726 0.002191 0.000737 0.083122 0.9900
1 XN  2 0.921487
RMSE ¼ h  hpre;i (17) 4 0.047956 0.002760 0.016249 0.9874
N i¼1 exp;i 5 0.035114 0.001480 0.000645 0.100511 0.9933
6 0.040334 0.001952 0.000972 0.107023 0.9911
7 0.035117 0.001480 0.000892 0.118847 0.9933
PN  2 8 0.035070 0.001476 0.000763 0.102663 0.9933
i¼1 hexp;i  hpre;i
c2 ¼ (18) 9 0.035095 0.001386 0.000155 0.004893 0.9933
Nn 10 0.029418 0.000974 0.000229 0.029095 0.9953
11 0.029247 0.000962 0.000244 0.029998 0.9953
12 0.167800 0.031676 0.129563 6.699714 0.9930
1 X
N  
 13 0.065453 0.004820 0.000045 0.011332 0.9766
MPE ¼ hexp;i  hpre;i hexp;i  100 (19)
N 14 0.073581 0.006091 0.000059 0.029376 0.9704
i¼1
15 0.073471 0.006073 0.000040 0.027806 0.9705
16 0.065324 0.004801 0.000108 0.005709 0.9767

1 X
N  
MBE ¼ hpre;i  hexp;i (20)
N
i¼1
model parameters.
The models showing the combined effect of temperature and
where hexp,i is the experimental viscosity, hpre,i is the predicted
concentration on viscosity of cellulose and the values of the model
viscosity, N is the number of data points and n is the number of

Table 2
Models showing the combined effect of temperature and concentration on viscosity of cellulose and values of model parameters.

Model 1 Model 2 Model 3

lnh ¼ K3CA3 þ K5CA5/T þ K7CA7T lnh ¼ K3CA3 þ K5CA5/T þ K8exp(A8C)T lnh ¼ K3CA3 þ K6exp(A6C)/T þ K7CA7T
K3 ¼ 0.0000034 (kg/m3)A3 K3 ¼ 4.648189 (kg/m3)A3 K3 ¼ 4.351418 (kg/m3)A3
A3 ¼ 4.117839 [e] A3 ¼ 0.001865 [e] A3 ¼ 0.044972 [e]
K5 ¼ 655.0075 K(kg/m3)A5 K5 ¼ 17.37174 K(kg/m3)A5 K6 ¼ 8.362366 K
A5 ¼ 0.042365 [e] A5 ¼ 43.81278 [e] A6 ¼ 0.066296 (kg/m3)1
K7 ¼ 0.005434 K1(kg/m3)A7 K8 ¼ 0.013536 K1 K7 ¼ 0.012583 K1(kg/m3)A7
A7 ¼ 0.011451 [e] A8 ¼ 0.005424 (kg/m3)1 A7 ¼ 0.029882

Model 4 Model 5 Model 6

lnh ¼ K3CA3 þ K6exp(A6C)/T þ K8exp(A8C)T lnh ¼ K4exp(A4C) þ K5CA5/T þ K7CA7T lnh ¼ K4exp(A4C) þ K5CA5/T þ K8exp(A8C)T
K3 ¼ 4.46853 (kg/m3)A3 K4 ¼ 4.501287 [e] K4 ¼ 4.190637 [e]
A3 ¼ 0.001904 [e] A4 ¼ 0.005614 (kg/m3)1 A4 ¼ 0.052354 (kg/m3)1
K6 ¼ 10000 K K5 ¼ 26.50706 K(kg/m3)A5 K5 ¼ 10.73362 K(kg/m3)A5
A6 ¼ 6.352374 (kg/m3)1 A5 ¼ 2.820219 [e] A5 ¼ 1.511501 [e]
K8 ¼ 0.013536 K1 K7 ¼ 0.012955 K1(kg/m3)A7 K8 ¼ 0.012310 K1
A8 ¼ 0.005430 (kg/m3)1 A7 ¼ 0.009856 [e] A8 ¼ 0.032759 (kg/m3)1

Model 7 Model 8 Model 9

lnh ¼ K4exp(A4C) þ K6exp(A6C)/T þ K7C T A7

lnh ¼ K4exp(A4C) þ K6exp(A6C)/T þ K8exp(A8C)T logh ¼ K3CA3/T ¡ K5CA5
K4 ¼ 4.498836 [e] K4 ¼ 4.416049 [e] K3 ¼ 501.565 K(kg/m3)A3 A3 ¼ 0.033787 [e]
A4 ¼ 0.005617 (kg/m3)1 A4 ¼ 0.008447 (kg/m3)1 K5 ¼ 1.438065 (kg/m3)A5
K6 ¼ 215.479 K K6 ¼ 10000 K A5 ¼ 0.0122704 [e]
A6 ¼ 2.135604 (kg/m3)1 A6 ¼ 6.437849 (kg/m3)1
K7 ¼ 0.012959 K1(kg/m3)A7 K8 ¼ 0.012766 K1
A7 ¼ 0.009475 [e] A8 ¼ 0.004895 (kg/m3)1

Model 10 Model 11 Model 12

logh ¼ K3CA3/T ¡ K6exp(A6C) logh ¼ K4exp(A4C)/T ¡ K5CA5 logh ¼ K4exp(A4C)/T ¡ K6exp(A6C)

K3 ¼ 518.271 K(kg/m3)A3 K4 ¼ 519.037 K K4 ¼ 523.772 K
A3 ¼ 0.012216 [e] A4 ¼ 0.002966 (kg/m3)1 A4 ¼ 0.004452 (kg/m3)1
K6 ¼ 1.493355[e] K5 ¼ 1.49576 (kg/m3)A5 K6 ¼ 1.508491[e]
A6 ¼ 0.003397 (kg/m3)1 A5 ¼ 0.013936 [e] A6 ¼ 0.005206 (kg/m3)1

Model 13 Model 14 Model 15

h ¼ K3CA3 ¡ K5CA5logT h ¼ K3CA3 ¡ K6exp(A6C) logT h ¼ K4exp(A4C) ¡ K5CA5logT

K3 ¼ 36.41702 mPa s(kg/m3)A3 K3 ¼ 42.891 mPa s(kg/m3)A3 K4 ¼ 42.8657 mPa s
A3 ¼ 0.117734 [e] A3 ¼ 0.001816 [e] A4 ¼ 0.000596 (kg/m3)1
K5 ¼ 13.99496 mPa s(kg/m3)A5 K6 ¼ 16.5978 mPa s K5 ¼ 16.5873 mPa s(kg/m3)A5
A95 ¼ 0.118825 [e] A6 ¼ 0.000557 (kg/m3)1 A5 ¼ 0.001638 [e]

Model 16

h ¼ K4exp(A4C) ¡ K6exp(A6C) logT

K4 ¼ 36.5626 mPa s K6 ¼ 14.0466 mPa s
A4 ¼ 0.030421 (kg/m3)1 A6 ¼ 0.030762 (kg/m3)1

[e]: dimensionless; h, mPas; T, K; C, kg/m3.

240 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245
constants (K3e8 ve A3e8) in Eqs. 11e16 are given in Table 2. Table 3
shows the statistical test results for models. As seen from Table 3,
model 10 and model 11 has the lowest RMSE, c2 values and the
highest regression coefficient values. In operations where both the
temperature and concentration change during the process, the
combined effect of temperature and concentration on the viscosity
of cellulose from grapefruit peel can be modelled by model 10 and
11. The constants in Table 2 assist in the calculation of viscosity of
cellulose from grapefruit peel within the temperatures and con-
centrations used in this work.
Fig. 2 illustrates the comparison of experimental viscosity and
predicted viscosity calculated by using model 11. The predicted
results agree reasonably well with experimental data (r2: 0.9953).
3.2. Flow behaviour of carboxymethyl cellulose
Flow curves for CMC solutions were obtained by fitting experi-
mental data (shear stress-shear rate) with power law, Bingham and
Casson models, which are the most frequently used for engineering
applications (Hecke, Nguyen, Clausse, & Lanoiselle, 2012; Singh &
Sharma, 2013; Sopade & Kiaka, 2001). These models being the
most widely used viscosity models in engineering analysis and
scientific computation are given below:

n
Power law model : trf ¼ m dVf dr


Bingham model : trf ¼ tB þ hB dVf dr

0:5
Casson model : t0:5
rf ¼ tC þ hC dVf dr
where m is the consistency index (mPasn) and n is the flow
behaviour index (dimensionless), tB and hB are the Bingham model
parameters, tC and hC are the Casson model parameters.
The values of model parameters of Power law, Bingham and
Casson equations were obtained by non-linear regression at
different temperatures and concentrations (Table 4).
Plots of trf versus dVf/dr and t0.5
rf versus (dVf/dr)
0.5
for
Bingham and Casson models, respectively give straight lines.
Intercept values (tB in Bingham model and tC in Casson model) are
yield stress which should be rather greater than zero. The power
law model fitted well the experimental data since tB in Bingham
model and tC in Casson model were nearly zero. Since the flow
behaviour index values were less from 1, the flow behaviour of CMC
Fig. 2. Comparison of experimental viscosity and predicted viscosity values of cellu-
lose from model 11.
solutions were pseudoplastic. Pseudoplasticity is believed to be
caused by the orientation of the CMC macromolecules as they align
in the direction of the shearing force (Rozema & Beverloo, 1974).
The power law model was used to characterize the flow behaviour
of CMC solutions. Similarly, power law model was used due to the
fact that consistency coefficient and behaviour index showed
excellent representation of the data for all range of shear rate used
in a work conducted by Cancela et al. (2005). Diaz and Navaza
(2003) noted that the rheological properties of CMC dispersions
were explained by power law model. Westra (1989) stated that the
rheological behaviour of CMC with xanthan gum was pseudo-
plastic. Lin and Ko (1995) stated that when the CMC solutions were
tested by a viscometer under the steady shear conditions, the vis-
cosities of CMC solutions versus shear rate exhibited a well-known
power-law region covering a wide shear rate range. Kelessidis et al.
(2011) stated that the experimental apparent viscosity data for the
CMC solutions of 0.4e2.0% fitted power law model.
Consistency index is a measure of the consistency of the sub-
stance. Flow behaviour index indicates the degree of non-
Newtonian characteristics of the fluid. Plots of calculated m
values against concentration at various temperatures are in Fig. 3.
The results indicate an increased consistency index with
increasing concentration at the same temperature. The consistency
index values at different concentrations were found to be insig-
nificantly different for all the temperatures considered (p > 0.05).
(21)
This was probably caused by the increase of particleeparticle
interaction (Vitali & Rao, 1982). Similar flow properties were
(22) observed for common fluids (Chakrabandhu & Singh, 2005;
Maskan & Go €g

üş, 2000; Sopade & Kiaka, 2001). The consistency
index showed a decreasing trend with increasing temperature,
(23)
which indicates a decrease in viscosity at higher temperatures. No
harmonious variation was observed at n values with increase in
temperature and concentration. Hassan and Hobani (1998)
expressed that the flow behaviour index is almost independent of
the concentration and temperature, unlike the consistency index.
The apparent viscosity as a function of the shear rate at 20
C
and concentrations of 15e35 kg/m3 is depicted in Fig. 4. Similar
behaviour was obtained at other temperatures (graphs not shown).
The plot of shear rate and shear stress for different concentrations
of CMC at 20
C is given in Fig. 5.
The apparent viscosity is inversely correlated to the shear rate,
which indicates that the samples exhibit shear-thinning flow
(Amin, Abadi, & Katas, 2014; Casas et al., 2000). Shear-thinning
behaviour is classically encountered with heterogeneous systems
containing a dispersed phase. The particles are linked together by
weak forces. When the hydrodynamic forces during shear are suf-
ficiently high, the interparticle linkages are broken, resulting in
reduction in size of the structural units that, in turn, offer lower
resistance to flow during shear (Mewis, 1979). The flow curves of
the CMC solutions exhibited a shear-thinning behaviour when
viscosity decreased with the increase in shear rate. The flow curves
of the CMC solutions are similar to those previously reported by
several researchers (Benchabane & Bekkour, 2008; Hojjat et al.,
2011; Valenza, Merle, Mocanu, Picton, & Müller, 2005). The
decrease in viscosity with increasing shear rate is mainly related to
the disentanglement of macromolecular chains under shear field
and breaking of possible structure in solution. The decrease in
apparent viscosity can be attributed to the break of macromolecular
aggregates (Almedia & Dias, 1997). At low shear rates, apparent
viscosity decreased more sharply. At high shear rates, apparent
viscosity decreased more slowly. Because viscosity is a measure of
resistance to flow, resistance to flow was less in high shear rates
due to breaking of aggregate.
As expected, the CMC solutions at higher concentrations
exhibited higher viscosity than the CMC solutions at lower
 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245 241

Table 4
Power law, Bingham and Casson model parameters for CMC at different concentrations and temperatures.

T (
C) C (kg/m3) Power law model Bingham model Casson model

n m (Pasn) r2 hB (Pas) tB (Pa) r2 tC (Pa)0.5 hC(Pas)0.5 r2

10
15 0.8822 0.1179 0.9966 0.0870 0.0400 0.9998 0.2802 0.0673 0.9988
20 0.8577 0.1347 0.9922 0.0938 0.0498 0.9994 0.2869 0.0848 0.9968
25 0.8480 0.1511 0.9937 0.1007 0.0679 0.9982 0.2957 0.1021 0.9979
30 0.8281 0.1749 0.9953 0.1078 0.1002 0.9966 0.3046 0.1262 0.9983
35 0.7999 0.1973 0.9965 0.1099 0.1349 0.9941 0.3044 0.1552 0.9967
20
15 0.8918 0.1012 0.9992 0.0753 0.0379 0.9998 0.2622 0.0622 0.9995
20 0.8822 0.1179 0.9966 0.0870 0.0400 0.9998 0.2802 0.0673 0.9988
25 0.8785 0.1342 0.9936 0.0987 0.0441 0.9996 0.2964 0.0747 0.9977
30 0.8771 0.1525 0.9961 0.1082 0.0692 0.9961 0.3118 0.0883 0.9969
35 0.8274 0.1794 0.9968 0.1095 0.1073 0.9964 0.3075 0.1281 0.9981
30
15 0.8817 0.0816 0.9980 0.0599 0.0290 0.9999 0.2487 0.0302 0.9917
20 0.8918 0.1012 0.9992 0.0753 0.0379 0.9998 0.2622 0.0622 0.9995
25 0.8822 0.1179 0.9966 0.0870 0.0400 0.9998 0.2802 0.0673 0.9988
30 0.8833 0.1419 0.9977 0.1045 0.0500 0.9998 0.3075 0.0767 0.9990
35 0.8664 0.1577 0.9970 0.1091 0.0728 0.9980 0.3125 0.0939 0.9977
40
15 0.7950 0.0797 0.9900 0.0467 0.0409 0.9990 0.1962 0.0906 0.9958
20 0.8954 0.0941 0.9962 0.0724 0.0266 0.9996 0.2570 0.0526 0.9985
25 0.8343 0.1135 0.9914 0.0742 0.0486 0.9995 0.2539 0.0869 0.9974
30 0.8769 0.1347 0.9938 0.0987 0.0441 0.9996 0.2964 0.0747 0.9977
35 0.8530 0.1508 0.9941 0.1023 0.0641 0.9993 0.2982 0.0972 0.9981
50
15 0.8591 0.0585 0.9970 0.0400 0.0268 0.9994 0.1894 0.0561 0.9990
20 0.8817 0.0816 0.9980 0.0599 0.0290 0.9999 0.2334 0.0562 0.9994
25 0.8527 0.0973 0.9979 0.0649 0.0466 0.9997 0.2379 0.0817 0.9994
30 0.8822 0.1179 0.9966 0.0870 0.0400 0.9998 0.2802 0.0673 0.9988
35 0.8735 0.1349 0.9939 0.0970 0.0499 0.9994 0.2939 0.0791 0.9979
60
15 0.7177 0.0584 0.9862 0.0271 0.0397 0.9988 0.1423 0.1058 0.9963
20 0.7950 0.0797 0.9899 0.0467 0.0409 0.9990 0.1962 0.0906 0.9958
25 0.8179 0.0934 0.9897 0.0586 0.0424 0.9990 0.2242 0.0842 0.9966
30 0.8390 0.1121 0.9895 0.0745 0.0457 0.9993 0.2551 0.0828 0.9966
35 0.8658 0.1218 0.9937 0.0867 0.0436 0.9996 0.2781 0.0734 0.9982

Fig. 3. Consistency index as a function of concentration of CMC (temperature (
C):

▫
-10, 20, C30, B40, :50, 60). ▵
concentrations for all temperatures due to the increase in the local
intermolecular interactions between the polymer chains. The
decrease in the viscosity is well-known and usually is explained by
an increase in thermal activity of molecules causing an increase in
molecule free volume and a simultaneous decrease in intermolec-
ular and/or intramolecular interactions (Abraham, Ratna,
Siengechin, & Karger-Kocsis, 2008). It was observed that the
apparent viscosity decreased with an increase at temperature for all
concentrations (graphs not shown). These changes in rheological
behaviour are likely due to inner structural changes in polymer
Fig. 4. Typical flow curves for different concentrations of CMC at 20
C (concentration
▵
(kg/m3): 15, :20, B25, C30, 35). ▫
solutions.
The Arrhenius model has been successfully used by many re-
searchers to describe the temperature dependency of rheological
parameters (Grigelmo et al., 1999; Hecke et al., 2012; Marcotte,
Taherian, Trigui, & Ramaswamy, 2001). The effect of temperature
on the apparent viscosity of CMC solutions at a specified shear rate
was determined by using the Arrhenius model. The non-linearized
form of equation (1) is:
242 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245

Table 5
Shear rate and flow activation energy relationship for CMC solutions.

Shear rate (s1) Ea (kJ/mol) r2

1.32 6.519e11.412 0.9458e0.9688

2.20 6.106e12.790 0.9291e0.9874
2.64 6.271e14.635 0.9824e0.9901
4.40 6.487e15.197 0.9519e0.9841
6.60 6.525e16.246 0.9537e0.9916
11.0 4.777e16.646 0.9084e0.9833
13.2 3.766e16.956 0.8359e0.9779

ho ¼ d1 expðε1 CÞ (26)

where d, d1, ε and ε1 are constants.

A single equation combining the effects of temperature and
Fig. 5. Plot of shear rate and shear stress for different concentrations of CMC at 20
C concentration on viscosity of CMC solutions would be useful.
▵
(concentration (kg/m3): 15, :20, B25, C30, 35). ▫ Incorporating Eqs. (25) and (26) into Eq. (24), the following models
involving the effect of concentration and temperature on viscosity
are obtained.

ha ¼ ho exp ðEa =RTÞ (24) ha ¼ dðCÞε expðEa =RTÞ (27)

where ha is the apparent viscosity with increasing shear rate
(mPas), ho is a constant(mPas), Ea is the activation energy of flow
(kJ/mol), R is the universal gas constant (8.314  103 kJ/mol K), T is
the absolute temperature (K).
Flow activation energies were determined from the plot of ln h
versus 1/T. An Arrhenius plot for shear rate of 6.6 s1 is given in
Fig. 6. Ea values increased with an increase in the concentration of
CMC and show a change in slope with an increase in concentration.
The change in activation energy values of CMC solutions at
concentrations ranging from 10 kg/m3 to 35 kg/m3 for different
shear rate is given in Table 5. Activation Energy, Ea, is important in
deducing the sensitivity of a process towards temperature. The
higher the activation energy, the more sensitive process will be
(Singh & Sharma, 2013).
The concentration dependency of the viscosity at each tem-
perature was examined using a power-law model and an expo-
nential model (Vitali & Rao, 1982). These equations can also be used
for ho. ho are function of concentration and can be described as
below:
ho ¼ dðCÞε
Fig. 6. Arrhenius plot for CMC at shear rate of 6.6 s1 (concentration (kg/m3):
:20, B25, C30, 35).▫
ha ¼ d1 expðε1 CÞexpðEa =RTÞ (28)
These rheological models would be useful to predict the
apparent viscosities of CMC from grapefruit peel at different con-
centration and temperature values. The statistical package, Statis-
tica for Windows 5.0, was used to perform the nonlinear regression
analysis of experimental viscosity data. The various statistical pa-
rameters such as root mean square error (RMSE), chi-square c2,
mean bias error (MBE), mean percentage error (MPE), modelling
efficiency (EF) and r were used to determine the goodness of the fit.
Parameter EF was calculated as following:
PN  2 P  2
i¼1 hexp;i  hexp;ave  N i¼1 hpre;i  hexp;i
EF ¼ PN  2 (29)
i¼1 hexp;i  hexp;ave
where hexp,i is the experimental viscosity, hpre,i is the predicted
viscosity, hexp,ave is the average of the experimental viscosity
values, N is the number of data points.
Estimated constants of the Eqs. (27) and (28) and values of
(25) RMSE, c2, MBE, EF and r are presented in Tables 6 and 7,
respectively.
Statistical analysis indicated that Eq. (27) is more adequate than
Eq. (28) in fitting apparent viscosity data as a function of temper-
ature and concentration. The higher the values of the EF and r, the
better the goodness of the fit. The lower the values of the RMSE, c2
and MBE, the better the goodness of the fit. The results have shown
that highest values of EF and r and the lowest RMSE, c2 and MBE
values could be obtained with the statistically fitted model of Eq.
(27).
Validation of the established model was evaluated by comparing
the computed apparent viscosity values with the observed
apparent viscosity values. The performance of the model was
illustrated in Fig. 7 (r2:1). The predicted data generally banded
around the straight line which showed the suitability of the Eq. (27)
in describing rheological behaviour of CMC solutions from grape-
fruit peel.
The data obtained in this study are applicable only in designing
equipment for handling of CMC solutions at the temperature range
studied. The apparent viscosities at the other temperatures and
▵15, concentrations in the ranges of temperatures and concentrations
examined in this study can be obtained by using constants in the
 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245 243

Table 6
The combined effect of temperature and concentration on apparent viscosity of CMC solutions (Eq. (27)).

Shear rate (s1) ha ¼ d(C)ε exp(Ea/RT)

d mPas(kg/m3)ε ε [] Ea (kJ/mol) Statistical tests

1.32 0.5211 0.7700 7.6076 RMSE ¼ 5.9873; c2 ¼ 39.830

MBE ¼ 0.1260; EF ¼ 0.9713 r ¼ 0.9855
2.20 0.5688 0.7020 7.5698 RMSE ¼ 5.8662; c2 ¼ 38.235
MBE ¼ 0.1394; EF ¼ 0.9594 r ¼ 0.9795
2.64 0.4768 0.6793 7.9972 RMSE ¼ 5.6744; c2 ¼ 35.776
MBE ¼ 0.6401; EF ¼ 0.9561 r ¼ 0.9780
4.40 0.4108 0.7311 7.8285 RMSE ¼ 5.9783; c2 ¼ 39.711
MBE ¼ 0.1836; EF ¼ 0.9506 r ¼ 0.9750
6.60 0.3370 0.7498 8.0842 RMSE ¼ 6.0607; c2 ¼ 40.814
MBE ¼ 0.1946; EF ¼ 0.9487 r ¼ 0.9740
11.00 0.5073 0.6943 7.4337 RMSE ¼ 7.1841; c2 ¼ 57.346
MBE ¼ 0.2386; EF ¼ 0.9155 r ¼ 0.9568
13.20 0.7103 0.6490 6.8801 RMSE ¼ 7.9500; c2 ¼ 70.225
MBE ¼ 0.2318; EF ¼ 0.8802 r ¼ 0.9382

Table 7
The combined effect of temperature and concentration on apparent viscosity of CMC solutions (Eq. (28)).

Shear rate (s1) ha ¼ d1exp(ε1C)exp(Ea/RT)

d1 (mPas) ε1 (kg/m3)1 Ea(kJ/mol) Statistical tests

1.32 2.7692 0.0309 7.6191 RMSE ¼ 6.6017; c2 ¼ 48.425

MBE ¼ 0.1282; EF ¼ 0.9651 r ¼ 0.9824
2.20 2.5787 0.0285 7.5872 RMSE ¼ 5.7041; c2 ¼ 36.152
MBE ¼ 0.1518; EF ¼ 0.9616 r ¼ 0.9806
2.64 2.0545 0.0274 8.0194 RMSE ¼ 6.0362; c2 ¼ 40.484
MBE ¼ 0.2245; EF ¼ 0.9503 r ¼ 0.9748
4.40 1.9928 0.0295 7.8498 RMSE ¼ 6.2135; c2 ¼ 42.898
MBE ¼ 0.3351; EF ¼ 0.9467 r ¼ 0.9730
6.60 1.7060 0.0302 8.1048 RMSE ¼ 6.3447; c2 ¼ 44.728
MBE ¼ 0.3616; EF ¼ 0.9438 r ¼ 0.9715
11.00 2.2832 0.0279 7.4488 RMSE ¼ 7.6075; c2 ¼ 64.305
MBE ¼ 0,3344; EF ¼ 0.9053 r ¼ 0.9515
13.20 2.8942 0.0260 6.8987 RMSE ¼ 8.3906; c2 ¼ 78.225
MBE ¼ 0.1864; EF ¼ 0.8666 r ¼ 0.9309

The empirical Weltman model has been used to model time-

dependent flow behaviour of natural food products to describe
the thixotropic behaviour of CMC solutions (Battacharya, 1999;
Hecke et al., 2012; Weltman, 1943).

ha ¼ AþB lnðtÞ (30)

Fig. 7. Comparison of experimental apparent viscosity and predicted apparent vis-
cosity values of CMC from equation (27).
derived model given for each shear rate in Table 6.
Hydrocolloid solutions may exhibit time-dependent properties,
mainly thixotropy. When a material is sheared at a constant shear
rate, the viscosity of a thixotropic material will decrease over a
period of time, implying a progressive breakdown of the structure
(Abu-Jdayil & Mohameed, 2004). Modelling of the thixotropic
behaviour has been based on equations such as Weltmann, first-
order stress decay models and structural kinetic model
(Karazhiyan et al., 2009).
where t is the shearing time (s), A (mPas) and B (mPas) are the
Weltman constants.
Time-dependent flow properties of CMC solutions were
assessed by examining apparent viscosity versus shear time in
Weltman model. CMC solutions were sheared at constant shear rate
of 6.60 s1 and the apparent viscosities were recorded as a function
of shearing time until a steady state was reached. The apparent
viscosity of CMC solutions as a function of time for spindle speeds
of 30 rpm (shear rate: 6.60 s1) at concentrations from 15 kg/m3 to
35 kg/m3 and 30
C is shown in Fig. 8.
At a constant spindle speed, the apparent viscosity decreased
with time. Towards the end of the 6 min shearing period, the
apparent viscosity tended towards a plateau. From these results,
the CMC solutions were found to be slightly thixotropic. Ghannam
and Esmail (1997) have shown that the CMC dispersions exhibited
thixotropic and viscoelastic behaviour at high CMC concentrations.
Similar thixotropic behaviour was found for amorphouse cellulose
suspensions (Jia et al., 2014) and carrot puree (Hecke et al., 2012).
Dolz, Jimenez, Hernandez, Delegido, and Casanovas (2007) stated
that the CMC solutions having different concentrations showed
thixotropic behaviour.
244 M. Karataş, N. Arslan / Food Hydrocolloids 58 (2016) 235e245
Fig. 8. Apparent viscosity of CMC as a function of shearing time at 30
C for shear rate
▵
of 6.6 s1 (concentration (kg/m3): 15, :20, B25, C30, 35). ▫ (Musa cavendishii Lambert). Carbohydrate Polymers, 62(2), 164e169.
Table 8
Weltman model parameters for different CMC concentrations.
C (kg/m3) A (mPas) B (mPas)
15 0.9118 67.723
20 1.0943 85.364
25 1.1935 96.682
30 1.3602 118.230
35 1.8261 132.170
Weltman model parameters used to describe the change in
apparent viscosity with shearing time for different CMC solutions
are showed in Table 8 A and B constants characterize the time
dependent behaviour of CMC. It was found that an increase in the
CMC concentration caused a decrease in magnitude of A, which is
an indication of resistance of the fluid against the flow. A zero value
of B (the coefficient of breakdown) indicates that the apparent
viscosity of the fluid is independent of time (Abu-Jdayil, Azzam, &
Al-Malah, 2001). A negative B value measures the degree of
destruction of aggregates arising from shear rate. In other words, it
measures how fast the apparent viscosity drops from the initial
value to the final equilibrium value (Abu-Jdayil & Mohameed,
2004). The magnitude of B increased with increasing concentration.
4. Conclusions
The isolated cellulose from grapefruit peel was converted to
CMC by etherification using sodium monochloroacetic acid and
NaOH. The empirical equations were developed to predict the
viscosity of cellulose from grapefruit peel as a function of temper-
ature and concentration. CMC solutions exhibited shear thinning or
pseudoplastic rheological behaviour that was well described by the
power-law model with a consistency index and a flow behaviour
index lower than 1. It was found that the consistency index values
increased with the concentration while the opposite trend was
observed with temperature. For the prediction of the apparent
viscosity of CMC solutions, a power law and exponential models for
concentration and the Arrhenius relationship for temperature were
combined to simultaneously describe the effects of concentration
and temperature. The model with the best performance can be
applied to predict the apparent viscosity of CMC solutions. The
activation energy calculated with the Arrhenius model indicated
that CMC solutions were most sensitive to temperature change at
low shear rates. The time-dependent viscosity decreased rapidly
with time and reached an equilibrium state. CMC solutions were
adequately described by the Weltman model. CMC solutions
exhibited a thixotropic flow behaviour at all the concentrations.
This study provides essential data for design of processes relating
CMC solutions from grapefruit peel within the temperatures
(10e60
C), the concentrations (15e35 kg/m3) and the shear rates
(1.32e13.2 s1) studied.
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