Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Enhanced adsorption of synthetic dyes from aqueous solution by a

semi-interpenetrating network hydrogel based on starch
Ruma Bhattacharyya, Samit Kumar Ray *
Department of Polymer Science and Technology, University of Calcutta, 92, A.P.C. Road, Kolkata, 700009, India

A R T I C L E I N F O

Article history:
Received 5 October 2013
Accepted 19 December 2013
Available online 2 January 2014
Keywords:
Hydrogel
Network parameters
Isotherms
Kinetics
Thermodynamics

A B S T R A C T

Several semi-interpenetrating network (Semi-IPN) hydrogels were synthesized by free radical

copolymerization of acrylamide, hydroxyethyl methacrylate and N0 N0 -methylene bis acrylamide
crosslinker (MBA) in presence of starch. These hydrogels were characterized by FTIR, DTA-TGA, XRD and
SEM. The hydrogel showing the highest swelling% in water was used for removal of low (2.540 mg/L)
and high (200500 mg/L) concentration range of malachite green and methyl violet dyes from water. The
hydrogel showed high adsorption for both of these dyes. Isotherms, kinetics, mass transfer coefcients
and thermodynamics of dye adsorption were also studied.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
Synthetic dyes appear in wastewater from various industries
such as textiles, plastics, leather, dyestuff and paper. Most of these
organic compounds are common contaminants in wastewater.
Presence of even small amounts of these pollutants (<1 mg/L) in
water is highly visible [1]. It impedes transmission of sunlight into
water and upset biological activity of aquatic life [13]. Removal of
dyes from water by adsorption has been found to be one of the best
methods because of its high treatment efciency, easy recovery
and reusability of the adsorbents [4]. Among the various solid
adsorbents, hydrogel based on natural and synthetic polymers has
gained much attention in recent years [5]. Hydrogels are
synthesized by crosslinking synthetic or natural biopolymers.
The hydrogels made from most of the synthetic polymers are of
good mechanical strength but these polymers are expensive and
not biodegradable. On the other hand natural polymers are nontoxic, biodegradable, renewable and easily available in nature.
These polymers are also not expensive but hydrogels made from
natural polymers are of poor mechanical strength. Thus, hydrogels
are also synthesized by interpenetration of networks of both
natural and synthetic polymers.

Abbreviations: MBA, N, methylene bis acrylamide; FTIR, Fourier transformation

infrared spectroscopy; SEM, Scanning electron microscopy; XRD, X-ray diffraction;
DTA, Differential thermal analyzer; TGA, Thermo gravimetric analysis.
* Corresponding author. Fax: +91 33 23508386.
E-mail address: samitcu2@yahoo.co.in (S.K. Ray).

Interpenetrating network (IPN) of two functional polymers

results in formation of alloy of these polymers with properties
much better than its constituent polymers [6]. Semi-IPN is formed
by penetration of a linear (uncrosslink) polymer into the crosslink
network of another polymer without any chemical bond formation
between these two polymers [7]. Natural polymers like carboxymethyl cellulose or starch are highly hydrophilic but these
biopolymers are difcult to crosslink because of its ring structure
and tendency to undergo intramolecular reactions with multifunctional crosslinkers [8]. However, these polymers may be
incorporated in the crosslink network of another polymer to form
suitable hydrogels. Semi-IPN type hydrogels based on natural
polymers like starch and crosslinkable synthetic polymers have
been reported by many researchers. Semi-IPN type hydrogel of
starch and copolymer of sodium methacrylate and acrylamide was
reported to show high swelling and diffusion characteristic in
water [9]. Semi-IPN hydrogel was synthesized by entrapping
starch in polyacrylamide. This hydrogel was found to be a potential
sorbent for methylene blue cationic dye [10]. Semi-IPN hydrogel of
carboxymethyl cellulose and copolymer of acrylamide and
hydroxyethyl methacrylate (HEMA) was also reported for removal
of textile dyes from aqueous solutions [11].
From the above discussion it is evident that semi-IPN type
hydrogel based on a hydrophilic synthetic polymer/copolymer and
a biopolymer such as starch has been used for different
applications. Thus, in the present work starch has been incorporated in the copolymer hydrogel of acrylamide and hydroxyethyl
methacrylate (HEMA) crosslinked with MBA with varied comonomer, starch and crosslinker (MBA) ratios. The hydrogel showing
the highest swelling was used for adsorption of two important

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.12.071

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

industrial dyes i.e. malachite green and methyl violet from water.
Malachite green is a triphenylmethane dye widely used in
aquaculture to control fungal attacks, protozoan infections and
some other diseases. Because of low cost and easy availability it is
widely used in paints and printing ink. It is also used for coloring
leather, paper, cotton, silk, etc. However, it is toxic to major micro
organism and difcult to remove from water [12]. Methyl violet is
also an important industrial dye extensively used in textile and
paper industries [13]. Presence of traces of these two dyes in water
is a serious threat to environment. Both of these dyes may be
removed from water using suitable hydrogels. Thus, in the present
work the semi-IPN hydrogel was used for removal of low (2.540)
and high concentration (200500 mg/L) of these important dyes
from water.

2. Experimental
2.1. Materials
Monomers i.e. acryliamide (from Fluka), hydroxyethyl methacrylate (from Fluka), MBA (from Fluka), redox initiator pair i.e.
ammonium persulfate (from Fluka) and sodium metabisulte
(Merck), were of analytical grade and used without further
purication. Soluble starch was obtained from S.d. ne chemicals,
Mumbai and used as obtained. Malachite green and methyl violet
dye used in sorption studies were purchased from SRL Chemical,
India. The structure of methyl violet and malachite green dye is
shown in Fig. 1a and b, respectively. Double distilled water was
used for polymerizations, swelling and adsorption experiments.
2.2. Methods
2.2.1. Preparation of copolymer and starch incorporated semi-IPN
hydrogels
The hydrogels were synthesized by solution polymerization in a
three-necked reactor at 65 8C for 3 h. The reactor was tted with a
stirrer, a thermometer pocket and a condenser. For preparing the
copolymer gel the specied amounts of acrylamide, MBA and
hydroxyethyl methacrylate monomer were added to the three
neck reactor placed on a constant temperature bath. The
temperature of the reaction mixture was raised to 65 8C and
aqueous solution of initiators was added to the reactor. The starch
incorporated gels were prepared in a similar way by taking the
monomers, crosslinker and initiator in aqueous solution of starch.
The aqueous solution of starch (3%, w/v) was prepared in a
250 mL glass beaker by gradual addition of required amount of
starch to boiling water in several intervals with constant stirring
till a clear viscous solution is obtained. After polymerization the
reaction mixture was cooled to ambient temperature and mixed
with 50% aqueous methanol (to quench the reaction).

3715

2.2.2. Selection of hydrogel for adsorption study

By the above polymerization method several hydrogels were
prepared by varying initiator concentration, crosslinker (MBA)
concentration, comonomer ratios and wt% of starch. The crosslink
copolymer hydrogel of acrylamide and hydroxyethyl methacrylate
prepared with 1 wt% initiator, 1 wt% MBA and 5:1 comonomer
ratios (acrylamide: hydroxylethyl methacrylate molar ratio)
showed the highest swelling in distilled water and this copolymer
hydrogel was lled with 2, 4 and 6 wt% starch by in situ
incorporation of starch in the polymerization mixtures. The
hydrogel containing 4 wt% starch showed the highest swelling
in water and this hydrogel was used for studying adsorption of
malachite green and methyl violet dye from water.
2.2.3. Characterization of the hydrogels
Various functional groups of the hydrogels were characterized
by Fourier transform infrared (FTIR) spectroscopy using KBr pellet
made by mixing KBr with ne powder of the polymer gel samples.
(10:1 mass ratio of KBr to polymer). The surface morphology of the
hydrogels was characterized by scanning electron microscopy
(SEM, model no. EVO 18 made by Carl Zeiss, Germany) with the
accelerating voltage set to 15 kV. The change of crystallinity of
starch after its incorporation in the copolymer gel of acrylamide
and hydroxyethyl methacrylate was characterized by X-ray
diffraction (XRD). The wide angle X-ray diffraction prole of the
hydrogel samples was studied with a diffractometer (model: XPert
PRO, made by PANalytical B.V., The Netherlands) using Ni-ltered
Cu Ka radiation (l = 1.5418 A) and a scanning rate of 0.0058 ((2u)/
s). The angle of diffraction was varied from 2 to 728. Various
transition temperatures and thermal stability of the hydrogels
were evaluated by differential thermal analysis (DTA) and thermo
gravimetric analysis (TGA) in a Perkin Elmer instrument in
nitrogen atmosphere at the scanning rate of 10 8C per minute in
the temperature range of 60600 8C.
2.2.4. Swelling kinetics of the hydrogels
The dynamic swelling properties of the hydrogels were carried
out in distilled water at ambient temperature. The mass of the
swollen gel (Wt) was taken at different time intervals until there
was no change of mass with time. Each sample was weighed three
times and the average values of these three measurements were
taken. The swelling ratio (St) of the hydrogels was determined by
using the following Eq. (1)
St W tWW d
d

(1)

where Wd is the mass of the dry polymer, i.e., xerogel sample. The
amount of water adsorbed by the different hydrogels under
equilibrium conditions, also called equilibrium swelling ratio (Se)
was obtained when Wt did not change any more (We) with time,
i.e.,
Se W eWW d
d

(2)

The swelling ratio of the hydrogels at various time intervals (St)

was observed to t well to the following non-linear second order
rate Eq. (2a) [11]
St

S2ecal kS2 t
ro t

1 kS2 Secal t 1 kS2 Secal t

(2a)

Here, kS2 is rate constant, ro is initial rate of swelling and Secal is

calculated equilibrium swelling ratio.

Fig. 1. Structure, molecular weight and lmax of a) malachite green (Mol. Wt. 365,
lmax 614 nm) and b) methyl violet (Mol. Wt. 408, lmax 584 nm).

2.2.5. Diffusion kinetics of the hydrogels

For understanding the nature of diffusion of water through the
hydrogels, diffusion constant (kD) and diffusional exponent (n) was

3716

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

obtained from fractional water uptake (F) using the following

Eq. (3) [14].
Wt
kD t n
FW
e

(3)

Diffusion coefcient (D) of water through cylindrical hydrogels

of radius r was obtained from k and n using the following Eq. (4)
[14].
 1=n
k
D pr 2
4

(4)

2.2.6. Network parameter of the hydrogels

The average molecular weight between crosslinks (M c ) of the
hydrogel was obtained from the swelling data using the following
Flory and Rehner Eq. (5) [15].
 1=3

V s r f f=2
Mc  p p
(5)
2
ln1f p f p xf p

Here Vs is the molar volume of water obtained by dividing its

molecular weight with density (18.18 cm3/mol, at 25 8C). The
xerogels do not swell in toluene. Hence, the density of the xerogel
(r p ) was obtained by taking its weight in air (Wd) and in toluene
(Wtoluene) using the following Eq. (6a)

rp

W d rtoluene
W toluene

(6a)

Here rtoluene is density of toluene (0.87 g/mL at 25 8C). Volume

fraction of polymer, f p in the swollen gel under equilibrium is
obtained as


f p 1 rrwp Se

1

(6b)

Here rw is density of water. Interaction parameter between

polymer and water viz. x is obtained from the polymer volume
fraction using the following Eq. (6c) [16]

fp
3

hydrogels at equilibrium (qe, mg/g gel) and at time t (qt, for kinetic
study) was determined from the following Eqs. (9a and 9b),
respectively,

0:5

(6c)

qe C i  C e 

V
Wd

(9a)

qt C i  C t 

V
Wd

(9b)

where, Ci and Ce are initial and equilibrium dye concentration (mg/

L), respectively and Ct is dye concentration at time t, V is volume of
the dye solution and Wd is mass of the dry gel sample used for the
adsorption study. Similarly, dye removal% (R) was obtained as
R

C i  C e
 100
Ci

2.2.8. Dye adsorption kinetics

Adsorption of dye on hydrogel depends on physical and
chemical interaction between dye and hydrogel as well as
transport of dye from bulk solution to hydrogel surface. The
mechanism of dye adsorption is evaluated in terms of adsorption
kinetics by measuring adsorption at various time intervals (qt) till
equilibrium (qe) for a xed initial feed concentration of dye (Ci).
However, application of a single kinetic model is not sufcient to
explain heterogeneous nature of the adsorbent surfaces and also
diversity of the adsorption processes. The term pseudo is used for
rst and second order rate constant because of its dependence on
initial dye concentration [1]. In the present system dye adsorption
data were not found to give good tting to pseudo 1st order rate
kinetics (not shown). However, initial fast adsorption of dyes was
found to t well to the following non-linear Ho and McKay pseudo
second order kinetic Eq. (10) [20]. In the dye adsorption
experiments an initial rapid adsorption is usually followed by a
slower adsorption rate. For the slower adsoption process the
following McKay Eq (11) was used [21]. For evaluating diffusion
mechanism of dye adsorption, intra particle diffusion model
(Eq. (12)) of Weber and Morris [11,22] was also used

The crosslink density (rcross ) and mesh size (& mesh ) of the
hydrogel network is obtained using Eq. (7) [17] and Eq. (8) [18],
respectively.

qt

rcross rMp Nc A

(7)

ln

(8)

qt ki p t 1=2 c

& mess C n

2M c
Mr

i1=2

1=3

lf p

23

NA is Avagadros number (6.023  10 /mol). The Florys

characteristic ratio, Cn was taken from literature as 2 [19] and
CC bond length l was assumed as 1.54 A [5]. Mr, the molecular
weight of repeat unit was calculated as the weight average of the
repeat unit of starch (Mr = 162), polyacrylamide (Mr = 71) and
hydroxy ethyl methacrylate (Mr = 132).
2.2.7. Study of dye removal capacity of the hydrogels/adsorption
experiments
The adsorption of malachite green and methyl violet dyes was
studied by batch experiment. A known weight of gel sample
(Wd  0.5 g) was equilibrated with 100 mL aqueous solution of dye
of known concentration in a shaking bath. After equilibration, the
mixture was ltered and the nal concentration of dye was
determined by UV spectrophotometer. Each experiment of dye
adsorption was carried out three times and the average values of
these three measurements were taken. For kinetic study of dye
adsorption a small amount of the dye solution was withdrawn at
different time intervals. The amount of dye adsorbed by the

(9c)

q2e k2HM t
1 k2HM qe t

(10)

Ct
A  k2 C i t
Ci

(11)
(12)

where A is specic surface area of the adsorbent and k2 is rate

constant for the slower part of adsorption, kip is rate constant for
intra particle diffusion, c is intercept which signies boundary
layer resistance.
2.2.9. Dye adsorption isotherms
Adsorption isotherms are used to study the distribution of dye
molecules between solid hydrogels and aqueous phase at
equilibrium. Dye adsorption data at equilibrium (qe) for various
initial feed dye concentrations (Ce) were tted to the following
two-parameter Langmuir and Freundlich (Eqs. (13 and 14),
respectively), three-parameter Sip (Eq. (15)) and four parameter
FritzSchlunder isotherm (Eq. (16)) models [23]
max kL C e
qe q1k
L Ce

(13)

qe kF C e 1=n

(14)

qe

kS Ce S
b

1aS Ce S

(15)

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

qe

aFS Cea

(16)

1bFS Ce

where qmax is the maximum monolayer adsorption, kL, kF and kS are

Langmuir, Freundlich and Sip constant and n, a, bS, b, aFS, bFS, are
parameters concerning the respective model.
2.2.10. Mass transfer coefcient (kmtc)
Mass transfer coefcient of malachite green and methyl violet
dye molecules at hydrogelaqueous feed interface was determined
by using the following Eq. (17) [1].



 

Ct
1
wkL
1 wkL

ln

kmtc At
ln
C e 1 wkL
1 wkL
wkL

3.2. Characterization of the hydrogels

(17a)

Or
Ct
p expq  rt
Ce

(17b)

where p, q and r are constant such that p 1=1 wkL , q

lnwkL =1 wkL and r 1 wkL =wkL kmtc A.
Non-linear tting of t versus Ct/Ci to Eq. (17b) gives the values of
p, q and r from which kmtc was obtained.
2.2.11. Thermodynamic parameters
The thermodynamic distribution coefcient kd is obtained from
dye adsorbed at equilibrium (qe) and equilibrium feed dye
concentration Ce as [24]
q
kd e
Ce

(18)

Change in standard free energy (DG0 ) is also related to kd as

DG0 RTln kd

(19)

Further,

DG0 DH0  T DS0

0

Fig. 2(c). MBA being bifunctional copolymerize with both

acrylamide and hydroxyethyl methacrylate monomer to form
the crosslink network. During polymerization reaction starch is
incorporated in the copolymer network. In fact, macro radicals are
also generated in starch [9] and thus it also takes part in this free
radical polymerization to form the semi-IPN type structure as
shown in Fig. 2(c). The hydroxy (from starch and copolymer) and
carbonyl functional groups (from copolymer) of the IPN gels show
electrostatic interaction with dye molecules [5] as shown in
Fig. 2(d).

(17)

where w and A is mass and surface area of the adsorbent and kL is

Langmuir constant. Mass transfer coefcient may be obtained from
slope of the lnC t =C e  1=1 wkL versus t linear plot. However,
Ct < Ce and w or kL is very small. Hence, the above equation was
written as


Ct
 p q  rt
ln
Ce

3717

(20)

where DH and DS are change in standard enthalpy and entropy,

respectively.
3. Results and discussion

3.2.1. Fourier transform infrared spectroscopy (FTIR)

The FTIR of the polymer samples are shown in Fig. 3. It is
observed that the stretching vibration of amide carbonyl group of
acrylamide monomer at 1674 cm1 [26] is shifted to a lower
frequency, i.e., at 1648, 1668, 1664 and 1670 cm1, respectively
for the copolymer gel and the semi-IPN hydrogels containing 2, 4
and 6 wt% starch viz. S2, S4 and S6, respectively. This shifting of
amide carbonyl of acrylamide monomer to a lower frequency
indicate inter and intramolecular hydrogen bonding in the
polymer hydrogel [26]. The NH stretching of polyacrylamide
at 3170 cm1 [27] and OH stretching of hydroxyethyl methacrylate moiety at 3415 cm1 is overlapped through hydrogen
bonding (bridge) to 3197, 3234, 3322 and 3331 cm1 in the
copolymer, S2, S4 and S6, respectively. Similarly, the copolymer,
S2, S4 and S6 shows COC stretching peaks of ester group of
hydroxyethyl methacrylate moiety at 1191, 1123, 1122 and
1115 cm1, respectively. Most of the absorption peaks of starch
entrapped in S2, S4 and S6 are not seen because of screening by
absorption bands of copolymer [9]. The OH functional groups of
starch is observed to overlap in the region of 32343331 cm1
with OH and NH stretching of copolymer in S2, S4 and S6
samples.
3.2.2. X-ray diffraction (XRD) analysis
Inter and intramolecular hydrogen bonding among OH groups
results in crystallinity of starch. As starch is incorporated in the
network of copolymer gel of acrylamide and hydroxyethyl
methacrylate, its crystallinity is reduced due to intermolecular
hydrogen bonding between starch and the copolymer gel. From
Fig. 4 it is observed that starch shows crystalline peaks at 2u of 17.7
and 22.78 as also reported elsewhere [28]. The copolymer gel is also
observed to show a low XRD peak due to its polyacrylamide moiety
at 2u of 238 as also reported elsewhere [29]. In the semi-IPN viz. S2,
S4 and S6 crystalline peak of starch at 2u of 17.78 disappears while
2u of 22.78 of starch and 238 of polyacrylamide is shifted to around
218 indicating loss in crystallinity due to strong electrostatic
interaction among the functional groups of starch and the
copolymer.

3.1. Synthesis of IPN hydrogels

The copolymer hydrogel is formed by crosslink copolymerization of acrylamide, hydroxyethyl methacrylate and MBA while the
starch incorporated gel is formed by the same crosslink
polymerization in presence of starch. In this polymerization
reaction redox pair of initiator viz. ammonium persulfate and
sodium metabisulte was used since these initiator pair is reported
[25] to initiate free radical polymerization at ambient temperature.
These initiator pair generates radicals by a reduction/oxidation
(redox) reaction as shown in Fig. 2(a). The radicals from initiator
generate primary radicals from the three monomers, i.e.,
acrylamide, hydroxyethyl methacrylate and MBA as shown in
Fig. 2(b). These monomer radicals undergo propagation and
termination reaction to form crosslink copolymer as shown in

3.2.3. Differential thermal analysis (DTA) and thermo gravimetric

analysis (TGA)
The DTA and TGA of the starch, copolymer gel and the three
semi-IPNs viz. S2, S4 and S6 are shown in Fig. 5i and ii, respectively.
From Fig. 5i it is observed that the crosslink copolymer gel shows
an endothermic peak at around 90 8C which may be due to loss of
loosely bound water molecules from its network [30]. The
copolymer gel also shows two exothermic peaks at around 281
and 384 8C corresponding to its thermal degradation as also
reported elsewhere [30]. The starch is observed to show three
transition temperatures viz. onset (To), peak (Tp) and conclusion
(Tc) temperatures at around 44, 56 and 70 8C, respectively along
with exothermic degradation peaks at 270 and 213 8C as also
reported elsewhere [31]. These three transition temperatures are

3718

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

Fig. 2. a) Formation of initiator radicals, b) formation of IPN, c) IPNdye interaction.

absent in the copolymer gel but the S2, S4 and S6 are observed to
show these three transitions (marked with To, Tp and Tc in Fig. 5i)
with shifting at different temperatures indicating incorporation of
starch in the copolymer matrix as well as its strong interaction
with the copolymer. The TGA of these polymers are shown in
Fig. 5ii. Starch is observed to show three temperature zones for its
thermal degradation i.e. 70278 8C for around 5% degradation,

278380 8C for around 50% degradation and 380580 8C for around

70% degradation as also reported elsewhere [32]. The copolymer
gel degrades at a faster rate with more than 50% degradation in the
temperature range of 60280 8C. Because of incorporation of starch
the IPN hydrogels are observed to show much higher thermal
resistance with retention of more than 60% of its weight up to
around 250 8C. The three temperature ranges for degradation is

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

3719

Fig. 3. FTIR of the hydrogels.

Fig. 4. XRD of starch and the hydrogels.

also present in S2, S4 and S6 which conrms presence of starch and

also its strong electrostatic interaction with the copolymer in these
semi-IPN hydrogels.

crosslinker wt% in Fig. 7b. Similar kind of swelling curves were also
obtained for other hydrogels prepared with varied initiator
concentration, wt% of starch, comonomer ratios and also for S4
hydrogel in sodium chloride and calcium chloride salt solution (not
shown).

3.2.4. Scanning electron microscopy (SEM) analysis

The surface morphology of starch incorporated semi-IPN gels
viz. S2, S4 and S6 is shown in Fig. 6. The presence of the two phases
viz. dispersed phase of starch entrapped in continuous phases of
copolymer is evident from these SEMs. Hydrogel surfaces appear to
be rough and interspersed with many cracks. It is also observed
that phase morphology becomes coarser with increase in amount
of starch from S2 to S6.
3.3. Study of swelling properties of the hydrogels
The effect of various parameters like initiator and crosslinker
concentration, wt% of starch, comonomer composition and salt
solution on equilibrium swelling ratio is shown in Fig. 7a. The
equilibrium swelling ratios of the gels were obtained from
corresponding swelling curves obtained by plotting swelling ratio
at different time intervals. In general, swelling ratio increases with
time and after a certain time interval there is no further increase in
swelling ratio and it reaches an equilibrium value, i.e., equilibrium
swelling ratio as shown for hydrogels prepared with varied

3.3.1. Effect of initiator concentration on swelling

From Fig. 7a it is observed that equilibrium swelling ratio
increases with initiator concentration. In free radical polymerization molecular weight of the polymer (hydrogel in the present
case) decreases with increase in initiator concentration. Consequently, low molecular weight hydrogel with more chain ends are
obtained at higher initiator concentration which leads to network
imperfection in the gel and hence increased equilibrium swelling
ratio [33].
3.3.2. Effect of crosslinker concentration on swelling
From Fig. 7a it is observed that equilibrium swelling ratio
decreases with increase in crosslinker concentration. With increase
in crosslinker concentration the network becomes denser and thus,
swelling ratio decreases. However, increase in concentration of
bifunctional MBA also increases hydrophlicity of the hydrogel. This
may be the reason for marginal increase in equilibrium swelling
ratio for hydrogel containing 2 wt% crosslinker [34]. The gel

Fig. 5. i) DTA and ii) TGA of starch and the hydrogels.

3720

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

Fig. 6. SEM of S2, S4 and S6 hydrogels.

crosslinked with 0.5 wt% MBA showed the highest equilibrium

swelling ratio but it was not mechanically stable.
3.3.3. Effect of comonomer ratios on swelling
From Fig. 7a, it is observed that equilibrium swelling ratio also
increases with increase in amount of hydroxyethyl methacrylate
comonomer in the copolymer gel. The monomer hydroxyethyl
methacrylate contains hydroxyl (OH) and ester (COOR) groups.
Thus, with increase in molar concentration of hydroxyethyl
methacrylate, hydrophilicity of the gel increases resulting in
increased swelling. However, above 5:1 comonomer ratio, the gel
became too soft to be used.
3.3.4. Effect of starch on swelling
The hydrogel prepared with 5:1 molar comonomer ratio, 1 wt%
initiator and 1 wt% crosslinker was further lled with 2, 4 and
6 wt% starch (designated as S2, S4 and S6, respectively) in situ
during polymerization. From Fig. 7a it is observed that with
increase in wt% of starch, equilibrium swelling ratio increases
from S2 to S4 because of increased hydrophlicity of the hydrogels
in presence of starch. However, starch molecules also ll up the
network of copolymer gel resulting in less swelling by water [9]
and thus, the hydrogel containing the highest amount of starch
viz. S6 is observed to show much lower ESR than S2 or S4.
Accordingly, S4 hydrogel showing the highest equilibrium
swelling ratio (27.23) was chosen for subsequent dye adsorption
experiments.

3.3.5. Effect of salt on swelling

Swelling of hydrogel by diffusion of water into the gel network
depends on net osmotic pressure difference between the gel and
the external solution. The higher the pressure difference, the faster
will be diffusion of water into the gel and hence increased swelling.
In presence of salts like sodium chloride or calcium chloride net
osmotic pressure difference between gel and of external solution
decreases and hence swelling also decreases [35]. Thus, from
Fig. 7a it is also observed that for 0.1 and 1 normal (N) sodium
chloride and calcium chloride equilibrium swelling ratio for S4
hydrogel is observed to be 15.94, 11.22, 9.82 and 8.75, respectively,
i.e., calcium chloride decreases swelling to a greater extent than
monovalent sodium chloride. The lower equilibrium swelling ratio
of S4 in presence of calcium chloride may be attributed to its
increased ionic strength due to bivalent calcium ion.
3.3.6. Swelling kinetics
The swelling data of the various hydrogels were directly tted
to second order rate equation (Eq. (2a)) and the trend lines of these
non-linear ttings for varied crosslinker wt% are shown in Fig. 7b.
Similar ttings were obtained with other hydrogels. The various
swelling parameters such as initial swelling rate (r0), rate constant
(kS2) and calculated equilibrium swelling ratio (Secal) values along
with statistical parameters for these non-linear direct tting
(using Origin-8 software based on LevenbergMarquardt (LM)
algorithm where parameter values of a model are adjusted in
an iterative process using x2) such as r2, x2 and F values for

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

3721

30

25

ESR (-)

20

15

10

Initiator(I)

MBA

S
N 6
N
a
C
1
N l
0 . Na
1
N Cl
C
1 aCl
N
C 2
aC
l2

S4

0.
1

S2

1 I
0. .5%
5%
I
M
1% BA
1. MB
5% A
M
2% BA
M
B
10 A
A
:1
H
5A
:1
H
1A
:1
H

1%

0.
5%

Acrylamide(A):Hydroxyethyl methacrylate(H)

Starch

Salt

Swelling ratio(g/g gel)

b 25
20
15
10
5
0

2000

4000

6000

80 00

10000

Swelling time t (min)

Fig. 7. a) Effect of initiator, crosslinker (MBA), comonomer ratios, starch and salt on equilibrium swelling, b) swelling curves for varied crosslinker% and tting of swelling data
to second order rate equation and diffusion kinetics.

the hydrogels are shown in Table 1. For a good tting, r2 should

be close to unity, x2 will be low while F value will be high [36].
From Table 1 it is observed that calculated Secal is very close
to experimental Se for all of the hydrogels. The values of r2 are

also observed to be >0.95 for all of these ttings. Low x2 and high
F values are also observed. All of these clearly indicate close
tting of swelling data of the hydrogels to second order rate
equations.

Table 1
Swelling diffusion and network parameters of the hydrogels.
Polymer

kS2  105/r0  102

ESRexpt/ESRcal (g/g)

r2/x2/F

kD  102/n/D  105

r2/x2/F

Mc  107/rc  1018/mesh size

MBA0.5
MBA1.0
MBA1.5
MBA2.0

28/1.2
12/6.0
3.4/1.5
4.45/2.9

24.56/22.26
22.98/23
6.52/6.68
7.56/8.04

0.9815/8.6/923
0.940/9.1/221
0.992/0.04/2460
0.9851/0.16/978

2.5/0.4/1.3
2.3/0.49/8.8
7.6/0.29/0.4
11.2/0.26/0.2

0.9106/0.012/131
0.9833/0.013/477
0.9127/0.014/154
0.9554/0.013/272

2.22/0.03/511
1.75/0.04/444
0.03/2.96/36.7
0.05/1.63/52.6

I0.50
I1.0
I 1.5

20/12.7
12/6.0
71/19

15.7/13.86
22.98/23
24.5/22.42

0.9810/1.5/894
0.940/9.1/221
0.9453/8.6/220

6.2/0.3/1.93
2.3/0.49/8.8
16/0.2/0.14

0.9681/0.005/514
0.9833/0.013/477
0.9192/0.028/115

0.4/0.16/198.4
1.75/0.04/444
1.78/0.045/478

S2
S4
S6

4.7/1.5
12/6.0
38/1.0

11.4/17.87
22.98/23
4.74/5.78

0.9731/2.21/261
0.940/9.1/221
0.960/0.12/263

0.7/0.56/21
2.3/0.49/8.8
2.2/0.5/13.5

0.9541/0.01/227
0.9833/0.013/477
0.9771/0.003/453

0.14/0.3/101.7
1.75/0.04/444
0.007/10.3/17.2

10:1
5:1
1:1

0.00016/2.0
12/6.0
69/15

9.0/10.99.0
22.98/23
23.03/26.12

0.9501/0.5/191.7
0.940/9.1/221
0.8915/10.12/130

1.4/0.56/15
2.3/0.49/8.8
87/0.46/0.11

0.9651/0.004/271
0.9833/0.013/477
0.8953/0.013/271

0.06/1.15/62.4
1.75/0.04/444
0.001/54/6.3

S4NaCl0.1
S4NaCl1
S4CaCl0.1
S4CaCl1

10/0.5
20/1.8
0.95/0.01
33/4.69

15.9/16.8
11.22/9.33
9.82/8.61
8.75/10.88

0.998/0.01/311
0.9882/0.13/298
0.9751/8.15/278
0.99/0.009/1397

0.58/0.5/5
4.23/0.38/2.04
0.73/0.53/14
4.48/0.37/1.77

0.990/0.003/5200
0.975/0.003/571
0.970/0.02/471
0.99/0.0001/5907

0.04/0.15/204
0.13/0.53/98.4
0.08/0.84/74.7
0.05/1.27/24.6

I initiator, kS2 (g gel/g water, minute), r0 (g water/g gel, minute), kD (s1), n (), D (cm2/s), & (nm).

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

3.4. Dye adsorption

MG dye
MG dye removal%

MV dye
MV dye removal%

260
240
220
200
180
160
140
120

95
80
Dye removal%

Dye adsorbed (mg/g gel)

3.3.7. Diffusion and network parameters

To understand the mechanism of diffusion through the gel
network, diffusion characteristics viz. kD, n and D of the S4 gel was
obtained by non-linear direct tting of its swelling data at different
time intervals to Eq. (3) as also shown in inset of Fig. 7b for
hydrogels prepared with varied crosslinker%. Similar ttings were
also obtained for other hydrogels. The values of kD, n and D
(obtained from Eqs. (3 and 4)) along with the values of statistical
parameters for these non-linear ttings viz. r2, x2 and F values are
also shown in Table 1. The low x2, high F and r2 values close to
unity also suggest good tting of experimental swelling data to
Eq. (3) [11]. The value of kD signies the structure of the gel while
the value of n indicates mechanism of solvent transport through
the gel network. When diffusion is much slower than relaxation
during swelling, i.e., for Case I diffusion, n is 0.5 and k would be
proportional to diffusion coefcient over the initial sorption
experiment. Most of the hydrogels show Case I diffusion since the
value of n is very close to 0.5. The network parameters viz. average
molecular weight between crosslink (Mc), crosslink density (rcross)
and mesh size (& mesh ) of the hydrogels were obtained from its
swelling data using Eqs. (57) and these were also presented in
Table 1. In general a denser network will have lower Mc and & mesh
but higher rcross. The S4 gel containing 4 wt% starch was observed
to show very high ESR, Mc and & mesh value and hence it was chosen
for study of dye adsorption.

65
50
150

250

350

450

550

100
80
60
40
20
0

6
4
2
0

10

20

30

40

50

Feed conc. of dye (mg/L)

ii 180

Methyl violet 250 mg/L

160

Malachite green 250

mg/L

140

Qt (mg/g gel)

3722

120

100

80

Malachite green 2.5 mg/L

Methyl violet 2.5 mg/L

60
0

40

1000

2000

3000

4000

20
0

3.4.1. Effect of feed concentration on dye adsorption and removal%

Dye adsorption (qe, mg/g of gel) and removal% (R%) of the S4
hydrogel for both low (2.540 mg/L) and high (200500 mg/L)
range of feed concentration of malachite green and methyl violet
dyes are shown in Fig. 8i. Dye adsorption experiments were carried
out at pH 7 since above this pH there was no signicant increase in
dye adsorption (not shown). It is observed from Fig. 8i that the S4
hydrogel shows very high adsorption for these two industrially
important dyes. Thus, qe of 1.66 and 1.55.5 mg/L and R% of 2084
and 1881 is observed in the low concentration range of 2.5
40 mg/L of malachite green and methyl violet dye, respectively in
feed. Similarly, malachite green and methyl violet dye shows qe of
145233 and 137211 mg/L with R% of 6297 and 5691 over the
feed dye concentration range of 200500 mg/L. Both malachite
green and methyl violet dye are cationic dye and contain tertiary
amine groups (Fig. 1). Strong electrostatic interaction between
functional groups of starch and copolymer moiety of the hydrogel
and dye molecules results in high adsorption and removal% of
these dyes [5]. It is also observed that with increase in feed
concentration of dye adsorption increases while removal%
decreases. A given amount of hydrogel can adsorb a xed amount
of dye molecules. As the feed concentration increases, % of this
xed amount decreases with respect to increased feed concentration and hence dye removal% decreases at higher feed dye
concentration [37].
3.4.2. Effect of contact time on dye adsorption
Effect of contact time on dye adsorption for feed dye
concentration of 5 and 250 mg/L is shown in Fig. 8ii. It is observed
that dye adsorption for high feed concentration (250 mg/L) occurs
at a much faster rate than low feed concentration (5 mg/L). Thus,
equilibrium dye adsorption (qe, mg/g gel) occurs at around 700 min
for high feed concentration while it takes around 2800 min for low
feed concentration. Transport of dye molecules from bulk feed to
surface of hydrogel occurs by lm diffusion which in turn, passes
from surface in to interior of gel by pore diffusion. Hence, mass
transfer resistance in the interface between feed and hydrogel
surface is very important. At higher feed dye concentration mass

200

400

600

800

Contact time (min)

Fig. 8. Effect of i) feed concentration and ii) contact time on dye adsorption.

transfer resistance for transport of dye molecule is reduced with

much reduction in equilibrium time [37]. Dye adsorption by
hydrogel is governed by lm diffusion of dye molecules from
solution to surface of the hydrogels followed by pore diffusion into
the interior of the hydrogel [1]. At higher concentration range mass
transfer resistance for transport of dye molecules is reduced and
thus equilibrium time is reached much faster. From Fig. 8i or ii it is
also observed that for any feed concentration adsorption or
removal% of malachite green dye is marginally higher than methyl
violet dye. This may be due to presence of methyl substituents in
the structure of methyl violet dye (Fig. 1b) which may cause some
steric hindrance for approaching hydrogels and hence lower
adsorption [11].
3.4.3. Fitting of dye adsorption data to adsorption kinetics
3.4.3.1. Pseudo second order kinetics. From Fig. 9i it is evident that
for high feed dye concentration (250 mg/L) the initial dye
adsorption data (qt) at various time intervals (t) t well to Ho
and McKay pseudo second order rate equation (Eq. (10)). At the
later stage of adsorption when it becomes slower, McKay model
(Eq. (11)) is observed to show a good t for adsorption kinetics. For
low feed concentration (5 mg/L feed concentration, not shown)
similar good tting was also observed. It is also observed that the
calculated equilibrium adsorption value (qcal) based on pseudo
second order kinetics is close to experimental equilibrium value
(given in rst bracket with * in Table 2). The statistical parameters
for these adsorptions are also shown in Table 2. It is observed that
r2 for these ttings are close to unity with low x2 and high F values.
All of these conrm close tting to this model. Good tting of dye
adsorption data to pseudo second order kinetics also conrms
chemical adsorption involving electrostatic interaction between
dye molecules and hydrogels as rate controlling step [38].

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

MV high conc
MG high conc

120

qt (mg/g gel)

100
80

-1.8
-2.0
Ct -2.2
ln -2.4
Ci -2.6
-2.8
-3.0
80000120000160000
Cit

60
40
20
0

MG high
MV high

180
160
140
120
100
80
60
40
20

0 20 40 60 80 100120140160

qe mg/g gel

7
6
5
4
3
2
1
0

iii

100

10

200

300

10 15 20 25 30
t

t (min)
300
250
200
150
100
50
0

400

20
30
Ce (mg/L)

500

ii

q (mg/g gel)
t

140

3723

MGexpt
MVexpt
MGLangmuir
MVLangmuir
MGFreundlich
MVFrundlich
MGSip
SipMV
FSMG
FSMV

1/2

0.9
0.8
0.7
Ct 0.6
Ce 0.5
0.4
0.3
0.2
0.1

(min1/2)

iv

1.0
0.8
Ct
0.6
Ce
0.4
0.2

MG
MV

Low conc.

0 50010001500200025003000350
0

t (min)
High conc.
0 100200300400500600700800
t (min)

40

Fig. 9. Non-linear tting of adsorption data to i) Ho and McKay pseudo second order and McKay (shown in inset) kinetics, ii) intra particle diffusion, iii) experimental (in red)
and calculated (in black) adsorption data at varied feed concentration, iv) determination of mass transfer coefcient by non-linear tting of Eq. (17).(For interpretation of the
references to color in this gure legend, the reader is referred to the web version of the article.)

3.4.3.2. Intra particle diffusion. The mechanism of diffusion of dye

from water to hydrogel is explained by tting dye adsorption data
(qt) at square root of various time interval (t1/2) to intra particle
diffusion model (Eq. (12)) as shown for high (250 mg/L) feed
concentration in Fig. 9ii. From Fig. 9ii it is observed that intra
particles ttings show multi linearity which signies various
mechanisms for dye adsorption [3]. The rst linear region
corresponds to rapid external surface adsorption by boundary
layer diffusion of dye molecules while the second region
corresponds to intra particle diffusion. Equilibrium adsorption is
attained in the third and nal slow stage when concentration of
dye molecules decreases appreciably in feed. It is also observed
that none of the trend lines passes through origin and the values of
the intercept relates to thickness of boundary layer. The values of
kip (rate constant) and c (intercept) for both low and high feed dye
concentration along with statistical parameters viz. r2, x2 and F for
second phase of linearity is shown in Table 2. It is observed that
rate constant (kip) and intercepts (c) increases with increase in feed
dye concentration from 5 to 250 mg/L with decrease in external
mass transfer and increase in thickness of boundary layer [3].

feed concentration. The dimensionless separation factor, RL was

obtained as
RL

1
1 kL C i

(21)

where kL is Langmuir constant and Ci is initial dye concentration in

feed. For low and high feed dye concentration the values of RL were
0.020.3 and 0.0020.005, respectively which signies favorable
adsorption by Langmuir model. Freundlich isotherm relates to
surface heterogeneity. From Table 2 it is observed that the values of
Freundlich parameter 1/n < 1 which also indicates favorable
adsorption by this isotherm. The values of statistical parameters
viz., r2, x2 and F also indicate good tting of adsorption data to this
model.

3.4.4. Fitting of dye adsorption data to adsorption isotherms

3.4.4.2. Three and four parameter model. The dye adsorption data
were also tted to three parameter Sip and four parameter Fritz
Schlunder models. The values of these parameters are given in
Table 2 along with statistical tting parameters. It is evident that
both of these models show close tting of the experimental dye
adsorption data.

3.4.4.1. Two parameter Langmuir and Freundlich model. The equilibrium dye adsorption data (qe) at various feed dye concentration
(Ce) were tted to Langmuir and Freundlich model. Langmuir
isotherm assumes adsorption at homogeneous sites of the
hydrogels with negligible interaction among adsorbed dye
molecules. The maximum adsorption (qm) capacity of the hydogels
based on this isotherm appears to be close to experimental values
(given in rst bracket in Table 2 besides Langmuir values) for high

3.4.4.3. Validity of the models. Calculated dye adsorption data

based on these four models are compared with experimental
adsorption data in Fig. 9iii which also shows close tting of the
models. Comparing the statistical parameters and also Fig. 9iii, it is
evident that among the four models the Sip model gives best
ttings. For this model the values of R2 are also observed to be
0.9910.998 for both low and high concentration range of methyl
violet and malachite green dye. This may be because of the fact that

3724

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

Table 2
Parameter values of adsorption kinetics and adsorption isotherm models for low and high concentration of malachite green (MG) and methyl violet (MV) dye.
Model

MG low

MV low

MG high

MV high

Pseudo 2nd
qcal (mg/g)
k2 (g/mg min)
R2/x2/F
McKay k2
R2/x2/F

2 (2.66)*
7.5  104
0.991/0.007/645
1.8  105
0.984/2  105/62  103

1.58 (2.48)*
1.2  103
0.994/0.004/733
1.7  103
0.978/0.004/1300

210 (156)*
5.7  105
0.996/7.98/5112
1.8  103
0.99/0.002/3487

175 (164.23)*
8  105
0.9982/2.66/12391
8.4  104
0.98/0.001/6892

Intra particle
kp (mg/g min1/2)
c
R2/x2
F

0.006
0.247
0.9594/1.3  105
17440

0.018
0.103
0.9606/6.5  105
2510

2.77
75
0.9728/0.438
62134

2.65
61
0.9857/0.210
94439

Langmuir
kL (L/mg)
Qmax/Qmaxexpt
R2/x2/F
Freundlich. 1/n
kF (L/mg)
R2/x2/F

0.08
7.61(6.08)a
0.9856/0.069/785
0.45
1.18
0.9934/0.031/1724

0.107
6.194 (5.45)a
0.9680/0.11/373
0.433
1.133
0.9919/0.027/1480

0.003
388 (232.65)a
0.9991/5.81/20195
0.5
10.47
0.9976/15.47/7582

0.003
315 (210.67)a
0.9984/8.24/11869
0.431
14.02
0.9971/14.89/6572

1.08
0.600
0.067
0.9936/0.030/1184

1.11
0.319
0.100
0.9906/0.032/849

0.191
1.37
6.22E04
0.9992/4.55/17174

0.198
1.37
7.60E04
0.9983/0.71/7487

R2/x2/F

1.28
4.57E+06
0.426
18.46
0.9937/0.030/

1.75
0.544
0.4186
6.93E05
0.9865/0.046/

360
1639
0.02
1.28
0.9991/6.06/9680

22.20
3.49  1013
0.361
6.32
0.9986/7.2/6767

Mass transfer coefcient

kmtc (cm2/s)
R2/x2
F

3.55  106
0.9594/1.34  105
17,446

2.77  106
9606/6.5  105
2510

4.5  105
0.9859/6.23  104
164

3.54  105
0.9803/7.96  104
1146

Thermodynamic parameters
DG0b (kj/mol)
DS0/DH0

13.27, 12.82,11.84
0.07/34.92

13.38,12.80,11.95
0.072/35.17

13.82, 13.55, 13.34

0.024/21.12

13.98, 13.73, 13.41

0.029/22.67

Sip
kS (L/mg)

b
AS
R2/x2/F
FS
AFS
BFS

a
b

a
b

Experimental value.
DG0 at 303, 313 and 323 K.

Sip model is applicable for both low and high concentration range
of adsorbate. In fact, Sip model is a combination of Langmuir and
Freundlich model. At low concentration range it reduces to
Freuindlich isotherm while at higher concentration range it
predicts monolayer adsorption characteristic of Langmuir model.
Further, the model parameter values are governed by feed
concentration as in the present case [23].
3.4.5. Mass transfer coefcient (kmt)
Mass transfer coefcient for dye adsorption was obtained by nonlinear tting of dye adsorption data to Eq. (17b) as shown in Fig. 9iv.
The values of kmtc for low and high concentration of malachite green
and methyl violet are also shown in Table 2. In tune with
experimental dye adsorption data kmtc is also observed to be higher
for high concentration range for both malachite green and methyl
violet dye while malachite green dye shows higher kmtc than methyl
violet dye for both high and low feed dye concentration.
3.4.6. Effect of temperature on dye adsorption and thermodynamic
parameters
The change in standard free energy (DG0), standard enthalpy
(DH0) and standard entropy (DS0) for adsorption of low and high
concentration of malachite green and methyl violet dye were
obtained using Eqs. (1820). Thermodynamic distribution coefcient, kd at three different temperatures of 30, 40 and 50 8C were
obtained from dye adsorption at feed dye concentration of 250 mg/
L (high) and 5 mg/L (low), respectively using Eq. (18). DH0 and DS0

were obtained from slope and intercept of linear trendlines of DG0

versus absolute temperature (T) plot. Dye adsorption decreased at
higher temperature which indicates exothermic nature of adsorption. The values of DG0 at the three temperatures for low and high
concentration of malachite green and methyl violet dye are given
in Table 2. Negative values of DG0 conrm feasibility and
spontaneity of the dye adsorption process. Positive DS0 values
for this adsorption as given in Table 2 indicate increase in
randomness in the solid (gel)-dye solution interface during
adsorption. A negative DH0 value also conrms exothermic nature
of adsorption [39].
3.5. Reusability of the semi-IPN hydrogels
The dye loaded hydrogel samples were regenerated by
desorption in 0.1 molar nitric acid solutions to evaluate reusability
potential of the hydrogels. The hydrogel samples showed up to
98.5% desorption signifying electrostatic interaction between dye
and hydrogels [11]. The regenerated hydrogels were subjected to
ve number of repeated adsorption/desorption cycles without any
signicant change of adsorption% indicating efcient regeneration
and reusability of the hydrogels.
3.6. Comparison with reported work
The adsorption of malachite green and methyl violet dye by the
present semi-IPN hydrogels are compared with other reported

R. Bhattacharyya, S.K. Ray / Journal of Industrial and Engineering Chemistry 20 (2014) 37143725

3725

Table 3
Comparison of present work with reported data.
Name of hydrogel/Other adsorbent

Dye conc. in water

Adsorption performance Mg/g resin

Reference

Semi-IPN of sodium alginate and copolymer of SA and HEMA

Semi-IPN of CMC and copolymer of AM and HEMA

100 mg/L of MV
500 mg/L of MV
2.5 mg/L of MV
300 mg/L of MG
25 mg/L of MG
300 mg/L of MG
25 mg/L of MG
3 mg/L of MV
290 mg/L of MG
500 mg/Lof MV
250 mg/L of MG
2.5 mg/L of MG
250 mg/L of MV
2.5 mg/L of MV

90
284
1.72
95
10
55
10
0.135
21.2
4.22
164
2.66
156
2.47

[5]
[11]

Oil palm trunk ber

Rattan saw dust
Poly (AM-co-HEMA) Gel
Chitin hydrogel
Poly(VP-co-MA)
Semi-IPN of starch and copolymer of AM and HEMA
Semi-IPN of starch and copolymer of AM and HEMA

adsorbents in Table 3. From the data given in Table 3 it is observed

that dye adsorption by the hydrogels or other adsorbents (mg/g of
hydrogels) are strongly inuenced by feed concentration. Accordingly, rattan saw dust is observed to show 55 and 10 mg/g
adsorption of malachite green dye for 300 and 25 mg/L feed
concentration, respectively. Similarly, in the present work very low
(2.540 mg/L) and very high range (200500 mg/L) of feed dye
concentration was used. The present hydrogel is observed to show
much higher adsorption than most of the reported work for both of
these high and low range of feed concentration.

Several semi-IPN type hydrogels were synthesized by crosslink

copolymerization of acrylamide, hydroxyethyl methacrylate and
MBA (crosslinker) in presence of starch. Crosslinking, crystallinity,
presence of starch in the copolymer gel matrix of semi-IPNs and
interaction of dye molecules with functional groups of hydrogels
were characterized by FTIR, SEM, XRD and DTA-TGA. Swelling,
diffusion and network parameters of the hydrogels were evaluated. Hydrogel synthesized with 1 wt% initiator, 1 wt% MBA, 5:1
acrylamide and hydroxyehyl methacrylate comonomer ratio, and
4% starch (S4) was found to show the highest swelling. This
hydrogel also showed high adsorption and removal% of methyl
violet and malachite green dyes for both low and high concentration range from water. Adsorption for both of these dyes was
higher at high feed dye concentration range. However, adsorption
or removal% of malachite green was found to be higher than
methyl violet for both concentration ranges. Adsorption data were
observed to t well to pseudo second order kinetics and several
adsorption isotherms viz. Langmuir, Freundlich, Sip and FS models.
Dye adsorption was also found to be exothermic i.e. it decreased at
higher temperatures.
Acknowledgments
Authors are grateful to Council of scientic and industrial
research (CSIR) and Department of Science and Technology (DST),
Govt. of India for their nancial support to purchase UVvis
spectrophotometer and FTIR spectrophotometer used for the
present work.

[40]
[41]
[42]
[43]
Present work
Present work

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

4. Conclusion

[12]

[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]

G. Crini, Dyes Pigments 77 (2008) 415.

S. Azizian, M. Haerifar, H. Bashiri, Chem. Eng. J. 146 (2009) 36.
X. Han, W. Wang, X. Ma, Chem. Eng. J. 171 (2011) 1.
S. Chatterjee, S. Lee, M.W. Woo, Chem. Eng. J. 155 (2009) 254.
B. Mandal, S.K. Ray, Carbohydr. Polym. 98 (2013) 257.
D. Myung, D. Waters, M. Wiseman, P.E. Duhamel, J. Noolandi, C.N. Ta, Polym. Adv.
Technol. 19 (2008) 647.
L.H. Sperling, Interpenetrating Polymer Networks and Related Materials, Plenum,
New York, 1981.
R.A. Wach, H. Mitomo, N. Nagasawa, N.Y. Fumio, Radiat. Phys. Chem. 68 (2003)
771.
P.S. Keshava Murthy, Y. Murali Mohan, J. Sreeramulu, K. Mohana Raju, React.
Funct. Polym. 66 (2006) 1482.
E.S. Dragan, D.F. Apopei, Carbohydr. Polym. 92 (2013) 23.
R. Bhattacharyya, S.K. Ray, Poly. Eng. Sci. (2013), http://dx.doi.org/10.1002/
pen.23501.
B.H. Hameeda, M.I. El-Khaiary, J. Hazard. Mater. 154 (2008) 237.
R. Dhodapkar, N.N. Rao, S.P. Pande, T. Nandy, S. Devotta, React. Funct. Polym. 67
(2007) 540.
P.L. Ritger, N.A. Peppas, J. Controlled Release 5 (1987) 23.
R. Paul, J. John, J. Chem. Phys. 11 (1943) 512.
W. Xue, W. Champ, S. Huglin, Polymer 42 (2001) 3665.
K.B. Sunil, S. Surinderpal, React. Funct. Polym. 66 (2006) 431.
T. Canal, N.A. Peppas, J. Biomed. Mater. Res. 23 (10) (1989) 1183.
E.R. Morris, A.N. Cutler, S.B. Ross-Murphy, D.A. Rees, J. Price, Carbohydr. Polym. 1
(1981) 5.
Y. Ho, G. McKay, Proc. Biochem. 34 (1999) 451.
N.B. Ayar, B. Bilgin, G. Atun, Chem. Eng. J. 138 (2008) 239.
W. Weber, J. Morris, J. Sanit. Eng. Div. Am. Soc. Civil Eng. 89 (1963) 31.
K.Y. Foo, B.H. Hameed, Chem. Eng. J. 156 (2010) 2.
B. Kayranli, Chem. Eng. J. 173 (2011) 782.
G. Odian, Principle of Polymerization, third ed., John Wiley & Sons Inc, Singapore,
1991p. 198.
A.J.M. Al-Karawi, et al. Carbohydr. Polym. 83 (2011) 495.
J. Lin, Q. Tang, J. Wu, React. Funct. Polym. 67 (2007) 489.
Q. Wang, X. Hu, Y. Du, J.F. Kennedy, Carbohydr. Polym. 82 (2010) 842.
D.R. Biswal, R.P. Singh, Carbohydr. Polym. 57 (2004) 379.
C. Zhou, Q. Wu, Colloids Surf. B: Biointerfaces 84 (2011) 155.
Y. Tian, X. Xu, Z. Xie, J. Zhao, Z. Jin, Food Hydrocolloid. 25 (2011) 637.
V.A. Alvarez, A. Va zquez, Polym. Degrad. Stab. 84 (2004) 13.
C. Chang, B. Duan, J. Cai, L. Zhang, Eur. Poly. J. 46 (2010) 92.
P.S. Gils, D. Ray, G.P. Mohanta, R. Manavalan, P. Sahoo, Int. J. Pharma. Sci. 1 (2009)
44.
Y.X. Zhang, F. Wu, M. Li, E. Wang, Polymer 46 (2005) 7695.
X. Yang, B. Al-Duri, J. Colloid Inter. Sci. 287 (2005) 25.
G. Bayramoglu, B. Altintas, A.M. Yakup, Chem. Eng. J. 152 (2009) 339.
M. Al-Ghouti, M. Khraisheh, S.A. Ahmad, J. Colloid Interface Sci. 287 (2005) 6.
T.S. Anirudhan, A.R. Tharun, Chem. Eng. J. 181 (2012) 761.
B.H. Hameed, M.I. El-Khaiary, J. Hazard. Mater. 159 (2008) 574.
R. Bhattacharyya, S.K. Ray, B. Mandal, J. Ind. Eng. Chem. 19 (2013) 1191.
H. Tang, W. Zhou, L. Zhang, J. Hazard. Mater. 209210 (2012) 218.
D.S. Olpan, Z.K. Lge, Radiat. Phys. Chem. 75 (2006) 120.