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Removal of dye by carboxymethyl cellulose, acrylamide and graphene oxide

via a free radical polymerization process

Article  in  Carbohydrate Polymers · January 2017

DOI: 10.1016/j.carbpol.2017.01.094

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 Carbohydrate Polymers 164 (2017) 186–194

Contents lists available at ScienceDirect

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

Research paper

Removal of dye by carboxymethyl cellulose, acrylamide and graphene

oxide via a free radical polymerization process
Kokkarachedu Varaprasad a,∗ , Tippabattini Jayaramudu b,c , Emmanuel Rotimi Sadiku c
a
Centro de Investigación de Polímeros Avanzados, CIPA, Avenida Collao 1202, Edificio de Laboratorios, Concepción, Chile
b
Center for Nano Cellulose Future Composites, Dept. of Mechanical Engineering, Inha University,100, Inha-Ro, Nam-Ku, Incheon 22212, South Korea
c
Department of Polymer Technology, Tshwane University of Technology, CSIR Campus, Building 14D , Private Bag X025, Lynwood 0040, Pretoria, South Africa

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

Article history: Carboxymethyl cellulose has been used for the design of novel engineered hydrogels in order to
Received 13 December 2016 obtain effective three-dimensional structures for industrial applications. In this work, dye removal
Received in revised form 24 January 2017 carboxymethyl cellulose-acrylamide-graphene oxide (CMC-AM-GO) hydrogels were prepared by a
Accepted 28 January 2017
free-radical polymerization method. The GO was developed by the modified Hummers method. The
Available online 31 January 2017
CMC-AM-GO and GO were characterized by FTIR, XRD and SEM. The swelling and swelling kinetics were
calculated using gravimetric process. The kinetic parameter, swelling exponent values [n = 0.59–0.7507]
Keywords:
explained the fact that the CMC-AM-GO hydrogles have super Case II diffusion transport mechanism.
Carboxymethyl cellulose
Graphene oxide
CMCx-AM-GO (x = 1–4) and CMC-AM hydrogels were used for removal of Acid Blue-133. The result
Hydrogels explains that composite hydrogels significantly removed the acid blue when compared to the neat hydro-
Dye removal gel. The maximum AB absorption (185.45 mg/g) capacity was found in the case of CMC2 -AM-GO hydrogel.
Therefore, cellulose-based GO hydrogels can be termed as smart systems for the abstraction of dye in
water purification applications.
© 2017 Elsevier Ltd. All rights reserved.

1. Introductions the adsorbent method, hydrophilic polymeric hydrogels can play a

Polysaccharide-based hydrogels, as adsorbents, have offered
new futures in the removal of pollutant from waste water (Khan
& Lo, 2015; Ngwabebhoh, Gazi, & Oladipo, 2016; Zhou, Hao, Wang,
& Ma, 2017). In general, water pollution occurs in many ways, but
a large amount of water pollution, as a result of many industrial
effluents, occurs through the contamination with inorganic, organic
and high volume of dyes and this causes the pollution of environ-
ment and the attendant health problems for living systems: plants,
humans and animals (Briggs, 2003; Khan & Lo, 2015). However,
the contamination of water by hazardous dyes has become a cru-
cial issue, worldwide due to their high toxicity, low degradability
and their persistent bioaccumulation (Sahraei & Ghaemy, 2017).
There are numerous techniques, such as: oxidation, catalytic degra-
dation and biodegradation, for the removal of pollutants (Khanday,
Asif, & Hameed, 2017). However, these techniques are more sen-
sitive and constant, however more time consuming, cumbersome,
tedious, expensive and laborious. Hence, a simple, sensitive, eco-
nomical and direct analytical process is the adsorbent method. In
∗ Corresponding author.
E-mail addresses: varmaindian@gmail.com, prasad@cipachile.cl (K. Varaprasad).
vital role in the removal of pollutant from the waste water (Sahraei
& Ghaemy, 2017). Hydrogels have three-dimensional, insoluble,
cross-linked and tissue-like network (He, Zhang, Cheng, & Wang,
2016; Raghavendra, Jayaramudu, Varaprasad, Mohan Reddy, &
Raju, 2015; Wang & Wang, 2016). These characteristics are use-
ful for water retention, high sorption capacity and the removal
of pollutants. In the development of such network, polysaccha-
ride polymers are more attractive than the synthetic polymers,
because of their functional properties, such as: good hydrophilicity,
biodegradation and biocompatibility (Paulino et al., 2006; Sharma
et al., 2015). Carboxymethyl cellulose (CMC) has been widely used
for the preparation of new engineered hydrogels (Kono et al., 2016;
Wang et al., 2017). This is because CMC is a biocompatible and
biodegradable natural anionic polysaccharide that can be highly
soluble in the water and thereby, increasing the viscosity of the
water (Abd El-Mohdy, 2007; Raafat, Eid, & El-Arnaouty, 2012). CMC
can be available as a sodium-carboxymethyl cellulose (polyelec-
trolyte) that can provide sorption characteristic to the hydrogels
(Abd El-Mohdy, 2007; Raafat et al., 2012; Wu, Lin, Zhou, & Luo,
2016). As a result of this property, it has been used in biomedical,
environmental and industrial applications (Abd El-Mohdy, 2007;
Zheng, Gao, Wei, Zhou, & Chen, 2015).

http://dx.doi.org/10.1016/j.carbpol.2017.01.094
0144-8617/© 2017 Elsevier Ltd. All rights reserved.
 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194
Recently, attempts to increase the adsorption performances
of polysaccharide hydrogels, resulted in the introduction of nano
adsorption materials into hydrogel network in order to remove
dyes from polluted water (Liu et al., 2016). Graphene oxide (GO),
at low concentration, is one of the good absorbents that is biocom-
patible and a non-toxic material, which can capture the inorganic
and organic pollutants through ␲-␲ or electrostatic interaction and
hydrogen bond (Liu et al., 2016; Piao, Wu, & Chen, 2016). GO has
large surface area, chemically stable and contains high amount of
functional oxygen (hydroxyl, epoxy and carboxyl) groups (Liu et al.,
2016). Due to its excellent physical and chemical properties, it has
been used in energy, biomedical and environmental fields (Wang
et al., 2014). Recently, Yang a et al. used graphene oxide to prepare
GO-based polyacrylamide hydrogels (Yang, Song, & Zhao, 2017).
Liu el al reported on GO-based CMC hydrogels. In their study, they
proved that the absorption and mechanical properties of the CMC
hydrogels were improved significantly by using of GO (Luan, Tien,
& Hur, 2015; Shi, Wang, Wu, Chen, & Feng, 2016; Yang et al., 2017).
In this investigation, CMC-AM-GO hydrogels were developed via
free-radical polymerizations by varying CMC concentration. The GO
was developed by the modified Hummers method and analyzed by
using: FTIR, XRD and SEM/EDS. The effects of CMC content in CMC-
AM-GO on the swelling ratio, swelling kinetics and removal of dye,
were investigated.
2. Materials and methods
Sodium carboxymethyl cellulose (CMC, CAS:9004-32-4),
Acrylamide (AM, CAS:79-06-1), N,N1 - methylene-bis-acrylamide
(MBA,CAS:110-26-9), Ammonium persulphate (APS, CAS:7727-54-
0), Acid blue 113 (AB, CAS: 3351-50-1), Potassium permanganate
(KMnO4, CAS:7722-64-7), Sodium nitrate (NaNO3 ,CAS:7631-99-
4), Sulfuric acid (H2 SO4, CAS: 7664939), Hydrochloric acid (HCL,
CAS:7647-01-0) and Ethanol (CAS:64-17-5) were obtained from
Sigma Aldrich, Chile. Natural graphite powder (CAS:7782-42-5)
was obtained from Merck Chemicals, Chile. Hydrogen peroxide
(H2 O2 ) solution was obtained from Furet, Chile.
3. Synthesis of graphene oxide
Graphene oxide was prepared from natural graphite powder
by a modified Hummers method (Guerrero-Contreras & Caballero-
Briones, 2015; Hummers & Offeman, 1958). 0.3 g of graphite was
added to 70 mL of concentrated H2 SO4 under stirring at ambient
temperature and then 1.5 g of NaNO3 was added and the mixture
was cooled to 0 ◦ C. Under vigorous agitation, 9 g of KMnO4 was
added slowly in order to keep the temperature of the suspension
below 20 ◦ C. Successively, the reaction system was transferred to a
water bath, maintained at a temperature of between 35 to 40 ◦ C for
about 0.5 h, thereby forming a thick paste. Then, 140 mL of water
was added and the solution was stirred for another 15 min. An addi-
tional 500 mL of water was added, followed by the slow addition of
20 mL of H2 O2 (30%), turning the color of the solution from brown
to yellow. The mixture was filtered and washed with a 1:10 (HCl:
H2 O) aqueous solution (250 mL) in order to remove metal ions, fol-
lowed by repeated washing with distilled water and centrifugation
in order to remove the acid. The resulting powders were dried and
stored for further characterizations.
4. Preparation of sodium carboxymethyl cellulose based
graphene oxide hydrogels
The synthesis of graphene oxide hydrogels was carried out via
a free-radical polymerization method (Scheme 1).
187
Firstly, different concentrations of CMC solution were prepared
by dissolving different amounts (0.05, 0.10, 0.15 and 0.20 g) in 5 mL
of cool distilled water in order to fast-dissolve the CMC under
constant stirring condition at 20 ± 2 ◦ C. To this solution, 10 mg of
graphene oxide and 0.5 mL ethanol (for a good GO distribution)
were introduced and stirred at a constant stirring condition and
then sonicated for 30 min in order to make the solutions homo-
geneous. In order to the prepared solutions, 14.06 m M of AM,
0.648 mM of MBA (as a cross-linker) and 2.191 m M of APS (as an
initiator) were added. The mixture was stirred for 5 min and kept
at a temperature of 20 ± 2 ◦ C for 30 min, in order to form a hydro-
gel matrix. Thereafter, the resulting hydrogels were immersed in
the distilled water and the distilled water was repeatedly changed
every 6 h to 48 h in order to remove the soluble impurities in the
hydrogel. In comparison, neat CMC-AM hydrogel was prepared
according to the same procedure, without using GO. The CMC-
AM and CMCX -AM-GO x = 1-4 hydrogel composites obtained, were
allowed to dry at a temperature 20 ± 2 ◦ C for 7 days. The composi-
tions of the hydrogels are presented in Table 1.
5. Material characterizations
FTIR spectra of CMC-AM hydrogels and CMC-AM-GO hydrogel
composites were obtained on Perkin Elmer, UATR two, FTIR spec-
trometer (Beaconsfield, Bucks, UK) in the wave number range of
4000–400 cm−1 . Signal averages were obtained from 25 scans at a
resolution of 1 cm−1 . The UV–vis spectra were recorded on UV-2600
(Shimadzu, Japan). Scanning electron microscopy (SEM) and Energy
dispersive spectroscopy (EDS) analysis for GO were carried out by
using JEOL JEM 7500F scanning electron microscope at a voltage
of 2 kV. The morphology and elemental analysis of the gold-coated
hydrogel composites were observed by using the scanning electron
microscope (SEM, JEOL 6460 LV) at an accelerating voltage of 10 kV.
Wide angle X-ray diffraction profile of GO was studied with a Rigaku
diffractometer with Cu-K␣ radiation (wavelength, ␭ = 0.1542 nm) at
a voltage of 40 kV and a current of 40 mA and using a scan rate of
0.02◦ s−1 .
5.1. Swelling process
CMC-AM and CMC-AM-GO hydrogel composites were measured
for their swelling characteristics. The CMC-AM and CMC-AM-GO
hydrogel composites were immersed in 25 mL distilled water in
a 100 mL beaker and the hydrogels weighed after removing the
surface water with filter paper at different intervals, from 0 to 140 h.
The swelling ratio was calculated using the equation:
 
Swellingratio S g = [W − W0 ] /W0 (1)
g
where W is the weight of the swollen hydrogel after swelling and
W0 is initial weight of the dry hydrogels.
6. Swelling kinetics
The swelling kinetics of the hydrogel composites were studied
according to previous reports (Guo, Zhou, & Lv, 2013; Varaprasad,
Reddy, Ravindra, Vimala, & Raju, 2011a; Varaprasad, Vimala,
Ravindra, Reddy, & Raju, 2011b). In order to study the control-
ling mechanism of the swelling processes, several swelling kinetic
models were used to test the experimental data. Among them, is a
simple kinetic analysis, a second order equation:
dS/dt = ks (Seq − S)2 (2)
where ks , Seq (or Seq %) and S refer to the swelling rate constant,
the equilibrium swelling (theoretical/swelling percent at equilib-
rium) and the swelling at any time, respectively. The combination
188 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194

Scheme 1. Schematic diagram of carboxymethyl cellulose-acrylamide-graphene oxide hydrogels development via freer radical polymerization method and adsorbent process
of hydrogels.

Table 1
The feed composition of the hydrogels.

Code sample AM (mM) CMC (g) MBA (mM) APS (mM) GO (mg) H2 O (mL) Ethanol (mL)

CMC-AM 14.084 0.10 0.648 2.191 – 6 0.5

CMC1-AM 14.084 0.05 0.648 2.191 10 6 0.5
CMC2-AM 14.084 0.10 0.648 2.191 10 6 0.5
CMC3-AM 14.084 0.15 0.648 2.191 10 6 0.5
CMC4-AM 14.084 0.20 0.648 2.191 10 6 0.5

of the above equation over the limits S = 0 at time t = 0 and S = Seq at
equilibrium time t = t, gives the following equation.
t
= A + Bt
S
where B (1/Seq ) is the converse of the maximum or equilibrium
swelling, A (1/ks , S2 eq ) is the initial swelling rate of the hydrogel
composite and ks is the swelling rate constant. In order to observe
the above kinetic model for these hydrogels, the graphs of t/S versus
t were plotted and the initial rate of swelling (ri ), swelling rate
constant (ks ) and the theoretical equilibrium swelling (Seq ) values of
the hydrogels were calculated from the slopes and the intersections
of the lines obtained from the graphs. The dynamics of the water
sorption process were investigated by monitoring the change in
the amounts of water imbibed by the hydrogel at various intervals.
(3) In the present diffusion study, the previous swelling results were
employed. For the kinetic analysis, the swelling results obtained
were utilized, only up to 60% of the swelling curves.
Swellingratio (S) = (WS − Wd ) /Wd = kt n (4)
Where S, Ws and Wd are the fraction swelling ratio at time t, the
weight of the swollen hydrogel at t and the weight of the dried
hydrogel at time t=0, respectively, k is a characteristic constant
 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194 189

Fig. 1. A) XRD B) FTIR spectra of GO, C) SEM and C1) EDS image of GO developed.

of the hydrogel and n is the swelling exponent, which indicates
the water transport mechanism. When n = 0.5, the release is Fick-
ian in nature and it is diffusion-controlled, whereas values of n
between 0.5-1.0 indicate non-Fickian diffusion (anomalous diffu-
sion). In anomalous diffusion, the diffusion and relaxation are said
to be isochronally effective. If n value is exactly equal to unity, then
the diffusion is designated as Case II diffusion. In very few cases, n
value is found to exceed unity and is called super Case II diffusion
(n > 1). In order to estimate the swelling exponent (n) by using the
above equation up to 60% of the swelling values, n S versus n t
graphs were plotted to obtain straight lines. The n was calculated
from the slope of the lines of n S versus n t plots.
The diffusion coefficient of these hydrogels was calculated by
using the short time approximation method. This method is valid
for the first 60% of the swelling results. The hydrogels diffu-
sion coefficients were calculated by using the following equation
190 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194

(Varaprasad, Ravindra, Narayana Reddy, Vimala, & Mohana Raju, Thanikaivelan, 2013). UV spectra and images were recorded at dif-
2010; Varaprasad et al., 2011b): ferent points. The (percentage) concentration of AB dye removal
and specific AB dye absorbed was calculated according to the fol-
S = 4D/r2 1/2 t 1/2 (5) lowing equations:

where D, r, S, and t represent the diffusion coefficient of the hydro- (C0 − Ce )

gel, the radius of the hydrogel, swelling ratio and time, respectively. Removalpercentage (%) efficiency = x100 (6)
C0
In order to investigate the D of hydrogels, S versus t1/2 plots were
obtained and the D values were calculated from the slopes of these (C0 − Ce )
AmountofABabsorbed = xV (7)
lines. The kinetic parameters data obtained are presented in Table 2. W
AB dye is an anionic water soluble acid dye; it was selected
where C0 (mg/L) and Ce (mg/L) are the initial and equilibrium con-
as the model dye to investigate the dye removal abilities of the
centrations at the time of measurement of the AB dye solution,
CMC-AM-GO and CMC-AM hydrogel composites. The dye stock
respectively; V is the volume of the AB dye solution and W (g) is the
solution was prepared by directly dissolving the AB dye in dis-
weight of hydrogel composites.
tilled water (100 mg/L, pH6). 100 mg hydrogel composite was
added into a 25 mL of the aqueous solutions of the dye and
it was allowed to immerse for 24 h at 20 ± 2 ◦ C for maximum 7. Results and discussion
removal of the dye. After the 24 h, absorbent was removed from
the swelling medium. For the AB dye solution, the concentration In this investigation, the modified Hummers method was
was determined via the absorption at ␭max 566 nm (molar extinc- employed to develop the GO. Fig. 1A shows the XRD pattern of the
tion coefficient was 16484.3 mol−1 cm−1 ) in the UV–vis spectra by GO developed. XRD data analysis of the GO showed a diffraction
using Shimadzu spectrophotometer UV-2600 (Japan) (Lučić et al., characteristic peak at 2 = 10.14◦ . Esfahani et al. observed similar
2014; Pandiyarajan et al., 2015; Preethi, Anumary, Ashokkumar, & type of GO peak in their report (Esfahani, Languri, & Nunna, 2016).

Fig. 2. FTIR spectra of hydrogels.

Fig. 3. SEM images of A) CMC-AM, B) GO-CMC2 -AM and C) GO-CMC4 -AM hydrogels.
 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194 191

Table 2
Swelling and diffusion data of the CMC-AM-GO hydrogels.

Hydrogels code Swelling Diffusion coefficient Initial swelling rate (ri ) Theoretical equilibrium Swelling rate constant
exponent (n) (D) cm2 s−1 [g water/g swelling (T Seq )[g (ks ) [(g hydrogel/g
hydrogel)/min water/g hydrogel)] water)/min]

CMC-AM 0.63 0.20839 0.05347 18.7020759 14.5542

CMC1-AM-GO 0.600 0.66937 0.0173 57.8034682 228.0354
CMC2-AM-GO 0.7507 1.26039 0.00866 115.4734 848.3557
CMC3-AM-GO 0.73049 0.71101 0.017 58.8235 250.3900
CMC4-AM-GO 0.595697 0.17849 0.0533 18.7617 33.2399

Adsorption experiments.

Fig. 1B shows the FTIR spectra of GO. The peaks at 1729 and
1153.75 cm−1 correspond to the stretching vibrations of C O and
C O in the C OH/C O C functional groups of GO, respectively
(Sharma & Kothiyal, 2015). The main peak at 1553 cm−1 corre-
sponds to the C O in the COOH unit in GO (Wang, Hao, Yang, Lu,
& Wang, 2009). The morphology and elemental composition of the
two-dimensional (graphene oxide) carbon material was analyzed
via SEM/EDS (Fig. 1C and C1). SEM images clearly show smooth and
layered structures of the GO nanosheets. The elemental analysis of
the GO synthesized shows high concentrations of C and O elements,
which are present in the pure GO sheets (Fig. 1C1).
The CMC-AM-GO hydrogels with variation in the concentration
of CMC and a constant 10 mg of GO were prepared by free radical
polymerization process. FTIR analysis revealed that the CMC-AM,
CMC2 -AM-GO and CMC4 -AM-GO hydrogels (Fig. 2) show the char-
acteristic functional groups of the CMC and AM units. In the FTIR
spectra of CMC-AM hydrogel, the emergence of peaks at 3345.90
and 3185.26 cm−1 , correspond to the N H stretching, the peaks
at 2981.23 and 2927.39 cm−1 refer to the C H stretching vibra-
tion. The peaks at 1646.82 (C O) and 1600.82 (-NH bending) cm−1
indicate amide I and amide II groups of the CMC-AM hydrogel,
respectively. The peaks at 1450.34, 1407.5 and 1321.83 cm−1 are
assigned to the scissoring of CH2 , symmetrical stretching of COO
and the twisting of CH2 units of the hydrogels (Mohy Eldin, Omer,
Soliman, & Hassan, 2013; Seki, Altinisik, & Tetik, 2014). The peak
at 1118.35 cm−1 is an important ( CH O-CH2 ) unit of CMC-AM
hydrogel. In the case of the GO impregnated hydrogels, it was
observed that the intensity of the peaks was decreased in the CMC-
AM2 hydrogel, but when the CMC concentration in the hydrogels
was increased, the peaks intensity of the hydrogels increased. The
results are explained thus: the deviation and the slightly shifted
peaks have been suggested to possess intertwined networks in the
GO hydrogel via oxygenated functional groups of the CMC with GO.

Fig. 4. Influence of CMC content on swelling behaviour of CMC-AM-GO hydrogels: (A) swelling ratio, (B) time (T)/swelling ratio (S) and Time (T), (C) Long S and Long T and
D) S and T1/2 graph of CMC-AM-GO hydrogels.
192 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194
Fig. 3 shows the SEM images of: CMC-AM, GO-CMC2 -AM and
GO-CMC4 -AM hydrogels. It is observed (Fig. 3A) that the surface
of the CMC-AM hydrogel has pores and smooth surface structures
when compared to other hydrogels. The pore structures arise from
the ethanol evaporation during the polymerization process. SEM
image of GO-CMC2 -AM (Fig. 3B) shows fewer pores and irregular
surface with 2D GO. However, with further increase of the CMC
content in the hydrogel, all pores disappeared in the GO-CMC4 -AM
hydrogels (Fig. 3C) and also the SEM image shows irregular network
structures with the 2D GO. This is due to the high concentrations
of CMC, which highly stabilized the 2D GO.
The effect of the CMC content in the CMC-AM-GO hydrogels
swelling behaviour (Fig. 4) was investigated by using the gravi-
metric method (Jayaramudu, Raghavendra, Varaprasad, Sadiku, &
Raju, 2013a; Jayaramudu et al., 2013b). Fig. 4A shows the swelling
ratio of the CMC-AM and CMC-AM-GO hydrogels. It was observed
that the increase in the CMC content in the (CMCx -AM-GO, x = 1,
2) hydrogels network, the swelling ratio of the hydrogels initially
increased the electrostatic repulsions of the CMC carboxylic func-
tional groups (hydrophilic) and also the hydrophilic functional
groups (carboxyl, epoxy and hydroxyl groups) of GO in the hydro-
gels, which can expand the 3D structure of the hydrogels (Sand,
Yadav, & Behari, 2010; Weber, Bradley, & Lonergan, 2014). In addi-
tion, it is believed that the electrostatic force can control the density
(3D) of the hydrogels (Hydrogels, Chang, He, Zhou, & Zhang, 2011).
Furthermore the encapsulation of GO can increase the density of
the hydrophilic groups on the hydrogels 3D network and produce a
positive result in the swelling ratio (Liu, Chen, & Jiang, 2011). It was
further observed that the swelling ratio of the GO-loaded hydrogels
Fig. 5. A) UV absorbance spectra of CMC2 -AM-GO hydrogel, B) CMC varied CMC-AM-GO (B = CMC-AM, 1 = CMC1 -AM-GO, 2 = CMC2 -AM-GO, 3 = CMC3 -AM-GO, 4 = CMC4 -AM-
GO) hydrogels influences on AB dye solution at 0 h and 24 h, C) AB removal rate by CMC-AM-GO hydrogels D) AB adsorption capacity with time for CMC varied CMC-AM-GO
hydrogels.
decreased with the increasing CMC content in the (CMCx -AM-GO,
x = 3, 4) hydrogels. This is due to the strong electrostatic interaction
between CMC, GO and the acrylamide functional groups that led to
the compressed 3D structure of the hydrogel, as observed in the
morphological (SEM) analyses. However, the swelling ratio values
of the GO hydrogels were found to display the following order:
CMC-AM (17.53 g/g) < CMC4 -AM-GO (18.19 g/g) < CMC3 -AM-GO
(51.20 g/g) < CMC1 -AM-GO (51.60 g/g) < CMC2 -AM-GO (90.30 g/g).
From the results, the swelling ratio of GO hydrogels depends
mainly, on the hydrogels composition. In this investigation, CMC
content played a key role in increasing and decreasing the
swelling ratio of the GO hydrogels. In order to further explore
the mechanisms of water diffusion of the CMC-AM-GO hydro-
gels, kinetic model studies were performed. The CMC-AM-GO
hydrogels swelling and diffusion kinetic parameters, such as:
initial swelling rate (ri ), swelling rate constant (ks ), theoretical
equilibrium swelling (TSeq ), swelling exponent (n) and diffu-
sion coefficient (D) were calculated from the dynamic swelling
ratio values. Fig. 4B provides the diffusion of water molecules
into the hydrogels, i.e. ri [0.00866–0.5347 (g water/g hydro-
gel)/min)], ks [14.5542–848.3557 (g hydrogel/g water)/min)], TSeq
(18.7020–115.4734) values. Fig. 4C and 4D afford n [0.59–0.7507]
and D [0.20839-1.26039 cm2 s−1 ] values, respectively. The n val-
ues specify that the swelling transport mechanism of CMC-AM and
CMC-AM-GO hydrogels were of super Case II diffusion in nature
(Argin, Kofinas, & Lo, 2014), which indicates that the diffusion
rate of water penetration into the composite hydrogels is faster
than the Case II diffusion and that the water transport process
was controlled by water diffusion rate and (AM and CMC) polymer
 K. Varaprasad et al. / Carbohydrate Polymers 164 (2017) 186–194
relaxation (Bueno, Bentini, Catalani, & Petri, 2013; Munday & Cox,
2000). The deflection of diffusion coefficient (D) and swelling expo-
nent (n) values, correspondingly depended on the concentration of
CMC and GO (cross-linking density) of the hydrogels, as observed in
the swelling ratio analysis (Fig. 4). The diffusion kinetic parameter
values are presented in Table 2.
Environmentally, the removal of dyes from wastewater is a very
important issue. The CMC-AM-GO hydrogels were tested for the
removal of AB dye from distilled water. Fig. 5A shows the CMC2 -
AM-GO hydrogel absorbance of the AB solutions, which decreases
to near zero, indicating the complete removal of the AB dye. Fig. 5B
displays the AB dye solution at 0 h and 24 h of the hydrogels and
CMCx -AM-GO (x=2, 3 and 4) show a clear solution at 24 h. Fig. 5C
shows the time-dependent removal rate of AB dye. It was found that
all hydrogels (%) removal rate of AB dye increased with time and
the excellent removal capacity was observed in the case of CMC-
AM-GO hydrogels when compared to CMC-AM hydrogel. As shown
in Fig. 5C, 33.56% AB dye was removed from the aqueous solution
by the CMC-AM hydrogels at 24 h (Scheme 1), whereas CMC-AM-
GO hydrogels removed between 47 to 99.97% of AB dye. This is
due to the specific surface area of graphene which can change the
electrostatic interaction of the hydrogels. However, it was found
that the initial AB dye removal capacity dramatically improved with
an increase in the CMC content in the CMC1 -AM-GO and CMC2 -AM-
GO hydrogels. Moreover, AB dye removal capacities decreased with
increase in the CMC content in the CMC3 -AM-GO and CMC4 -AM-
GO hydrogels. Similar, phenomena were observed in the swelling
study of the hydrogels.
The adsorption capacities of the hydrogels on AB dye are pre-
sented in Fig. 5D. CMC-AM and CMCX -AM-GO (x = 1–4) hydrogels
show the amount of AB dye absorbed in the trend: 62.25, 87.75,
185.45, 184.725 and 167.5 mg/g, respectively. The results obtained
are considerably better than the previously reported CMC and GO-
based hydrogels for the removal of dyes (Chen, Chen, Bai, & Li,
2013; Taleb, El-Mohdy, & El-Rehim, 2009) (Sahraei, Sekhavat Pour,
& Ghaemy, 2016). This phenomenon can depend on the free vol-
ume (3D) of CMC-GO hydrogels, which can increase the diffusion
of the dye and the swelling capacity of the hydrogels (Taleb et al.,
2009). However, it is noticeable that the amount of AB dye absorbed
was higher in GO-loaded hydrogels when compared to the neat
hydrogels.
8. Conclusion
CMC-AM-GO hydrogels with different concentrations of CMC
were synthesized by using the free radical polymerization process
and were characterized by FTIR and SEM. The required GOs were
synthesized via modified the Hummers method and analyzed via
XRD, FTIR and SEM/EDS analysis. The swelling characteristics of the
formation of CMC-AM-GO hydrogels mainly depend on the CMC
concentration in the hydrogels as the GO (hydrophilic) has little
effect. The results of the swelling ratio studies suggested that the
increase of CMC content from 0.05 to 0.10, the swelling ratio also
increases and after that (0.15–0.20), the swelling ratio decreases
for the CMC-AM-GO hydrogels. The swelling kinetic parameters
suggest that the hydrogels have super Case II diffusion transport
mechanism. The hydrogels developed were used to adsorb dye in
an AB dye solution. In this investigation, the CMC2 -AM-GO showed
excellent adsorption capacity for the removal of the dye from
the pollutant AB dye solution. Therefore, the CMC with GO-based
hydrogels can be a potential candidate for the removal of dyes as
well as for industrial applications.
193
Acknowledgements
The author, Kokkarachedu Varaprasad wishes to acknowledge
the FONDECYT de Iniciación Proyecto N◦ 11160073 and the Cen-
tro de Investigación de Polímeros Avanzados (CIPA), CONICYT
Regional, GORE BIO-BIO PRFC0002.
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