Separation Science and Technology

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Tuning of the swelling and dye removal efficacy of

poly(acrylamide-AMPS)-based smart hydrogel

Rabin Bera, Ayan Dey & Debabrata Chakrabarty

To cite this article: Rabin Bera, Ayan Dey & Debabrata Chakrabarty (2016): Tuning of the
swelling and dye removal efficacy of poly(acrylamide-AMPS)-based smart hydrogel, Separation
Science and Technology, DOI: 10.1080/01496395.2016.1251944

To link to this article: http://dx.doi.org/10.1080/01496395.2016.1251944

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SEPARATION SCIENCE AND TECHNOLOGY
http://dx.doi.org/10.1080/01496395.2016.1251944

Tuning of the swelling and dye removal efficacy of poly

(acrylamide-AMPS)-based smart hydrogel
Rabin Bera, Ayan Dey, and Debabrata Chakrabarty
Department of Polymer Science and Technology, University of Calcutta, Kolkata, West Bengal, India

ABSTRACT ARTICLE HISTORY

Hydrogels responsive to pH change based on poly(acrylamide-co-2-acrylamido-2-methylpropane Received 17 February 2016
sulfonic acid) are synthesized. The hydrogels are characterized in terms of FTIR spectroscopy, Accepted 19 October 2016
swelling–deswelling behavior, morphological analysis and dye removal properties. The swelling of KEYWORDS
the hydrogel is strongly dependent on the copolymer composition, pH and ionic strength of the Dye removal; hydrogel;
medium. The dye removal efficiency (DRE) also depends on the copolymer composition, pH and swelling; SEM
ionic strength. Pseudo-second-order kinetics and Langmuir isotherms model, respectively, are the
best-fit models for the present gel. The cellular structures of the hydrogels are clearly revealed by
optical microscopic and SEM images.

Introduction Ionisable pendant groups (mostly acidic or basic) pre-

sent in the monomeric units constituting the hydrogel
Fast growth of industrial civilization poses serious pro-
undergo ionization in the swelling medium to an extent
blems for municipal life due to emission of polluted
dependent on the pH and polarity of the medium. These
effluents in limit less proportions. Ahmed et al.,
types of hydrogels are known as polyelectrolyte hydrogels.
pointed out that dyes (mostly synthetic) constitute
Some examples of polyelectrolyte hydrogels are poly
major volume among the various polluted effluents
(acrylamide-co-maleic acid),[5,6] poly(acrylamide-co-ita-
because of its extensive applications in textiles, paper,
conic acid),[7] and poly(acrylamide-co-acrylic acid).[8]
plastics, rubber, concrete, etc.[1] Only textile industries
Poly acrylamide (Am) hydrogels are well known for its
are responsible for emitting about 10% of total dyes
biocompatibility, high water retention capacity and excel-
consumed globally. The review[1] states about the
lent swelling ability in water or aqueous solution and find
hazardous effect of such pollutant on environment
various applications in biomedical fields.[9] Different
and living beings. Possible pollutants present in the
modifications have been initiated by various groups of
waste water are described by X.C. Wang et al.[2]
scientists for introducing the responsiveness in the poly
Various dye removal techniques such as reverse
(AAm) (which by itself is non-responsive)-based gel by
osmosis, use of adsorbent like activated carbon, coagu-
various groups of scientists all over the world towards
lation, flocculation, oxidation, ozonization, etc., had
changes in the.[10,11] Cavas et al., successfully incorpo-
been employed in last few decades.[1,3,4] All of these
rated pH and temperature responsive character in the
orthodox processes suffer from disadvantages like
methacrylamide hydrogel by using 2-acrylamido-2-
energy requirement and lack in reusability, etc.
methylpropanesulfonic acid (AMPS).[12] Travas-Sejdic
In recent years, scientists are striving hard to find a low
et al., investigated the swelling properties of the gel in
energy intensive process for the above problem with
surfactant solution and measured the characteristic tem-
reasonable efficacy. However, all the processes mentioned
perature dependency of the swelling behavior.[13] Durmaz
above require energy resources and also are of limited
et al., also prepared poly (AAm) hydrogel with the
service life. Adsorption is one of the most economical and
sodium salt of AMPS by keeping the cross-linker and
easily applicable methods for use in the removal of
initial total monomer concentration constant [14] which
organic dye molecules. Cross-linked polymeric hydrogels
shows impressive thermo-responsive behavior in the aqu-
comprise a major group of adsorbents with potential to
eous medium.
remove organic dye molecules from wastewater.

CONTACT Debabrata Chakrabarty chakrabarty_deb@yahoo.com Department of Polymer Science and Technology, University of Calcutta, 92, APC
Road, Kolkata-700009, West Bengal, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsst.
© 2016 Taylor & Francis
2 R. BERA ET AL.

In view of the above problem, we hereby attempt to Table 1. Composition of the reactants used in preparing the
develop smart pH responsive hydrogel that is suitable for hydrogels.
dye removal from the effluent waste water of the textile Compositions (mol %)
industries with the least energy requirements. We Name of the samples Acrylamide AMPS MBA APS
AS0 100 0 1 0.1
hypothesize that the introduction of AMPS molecule as AS2 98 2 1 0.1
co-monomer along with AAm may impart the pH AS5 95 5 1 0.1
AS8 92 8 1 0.1
responsiveness behavior in poly (AAm) that can help AS10 90 10 1 0.1
in and the effective dye removal ability in the gel. The pH AS12.5 87.5 12.5 1 0.1
AS15 85 15 1 0.1
responsiveness may be expected to allow the gel to AS20 80 20 1 0.1
release the dye adsorbed by it, at a later stage. AS30 70 30 1 0.1
The objective of the present work is thus to address the
properties as mentioned above in the poly (Am-co-AMPS)
Table 2. Diffusion parameters of the hydrogel samples.
hydrogel. Here, stimuli responsive hydrogel based on poly
Order of Diffusion Diffusion Equilibrium
(Am-co-AMPS) has been synthesized by free radical poly- Hydrogels diffusion (n) constant (K) coefficient (D) swelling (%)
merization. The hydrogel samples have been characterized AS 0 0.5 4.5 3.974063 731
in terms of swelling–deswelling studies, morphological AS 2 0.5663 4.635759 4.074286 1661
AS 5 0.5816 4.6579 4.07975 2616
characteristics and dye removal behavior. Diffusion AS 8 0.6045 4.7 4.100062 2913
kinetics of the dye molecules into the gel has also been AS10 0.6365 4.802804 4.185325 3323
AS12.5 0.5744 3.58 2.588547 3191
measured. A structure property relationship also has been AS15 0.4778 2.865091 1.561778 2764
AS20 0.47 2.86512 1.543815 2711
investigated. AS30 0.48 2.8584 1.559173 2378

Experimental The hydrogels were then subjected to dry in 60°C for 48

Materials hours before performing several characterizations.

Am and AMPS were used as monomers. The former

was obtained from Loba Chemical Company, and the
latter was obtained from Merck. The other chemicals
were N,N’-methylenebisacrylamide (MBA) which was
used as a cross-linker and ammonium persulfate (APS)
used as initiator. These were obtained from E. Merck.
Besides these, buffer solution of pH 4, 7, 9.2 from
Merck were also used. Methyl violet and fuchsine dye
were obtained from Sigma.
Preparation of gels
Various hydrogels were synthesized by free radical poly-
merization reaction in aqueous medium. In all the cases
AAm, AMPS, MBA and ammonium persulfate were dis-
solved in water separately and then mixed. The total
monomer concentration was kept constant in each case
though the monomers were varied in their proportions.
Then, the solution was kept at 70°C for 5 hours under
constant stirring. The details of the monomers’ concen-
trations taken are given in Table 1. The viscous mass
formed at this stage was immediately transferred in sev-
eral test tubes kept in a cold water bath. Once the gel
material in the test tubes was sufficiently cooled; they were
extracted out and the thin slices of round-shaped gel
samples were cut out. The samples are then subjected to
frequent washing with double-distilled water to ensure
complete removal of residual monomer from the gels.
Characterization
Spectroscopic studies
ATR-FTIR measurements of the dried gels were carried
out by using a Nicolet 6700 (Madison, WI) FTIR spectro-
meter in the range of 4000–500 cm−1.
Swelling studies
Dried hydrogel samples have been allowed to swell in
distilled water at different temperatures and in buffer solu-
tions of different pH. The swollen gels have been taken out
at certain time intervals, wiped on its surface with tissue
paper and then weighed and the process is repeated until
the constant weight was reached. Equilibrium swelling was
measured from the following equation[12]:
Equilibrium swelling percentage
We  Wd
¼  100 (1)
Wd
where We is the weight of the swollen gel, and Wd is
the weight of the dry gel.
Deswelling studies
The gel samples were allowed to swell in distilled water
(pH 6.5) at room temperature (27°C) and then
immersed in pH 4 buffer solution to deswell (as all
the hydrogels under study swell in pH 4 medium to a
smaller extent compared to that in pH 6.5). At regular

time intervals, gel samples were taken out, wiped with
tissue paper on its surface and weighed again.
Water retention was measured by the equation:
Wt  W d
Water retention ¼  100% (2)
W
where Wt is the weight of the gel sample at time t,
Wd is the weight of the dry gel and W is the weight of
the water absorbed by the gel in fully swollen condition.
Dye removal study
Investigation relating to the efficiency in removing
organic dye (methyl violet and fuchsine) from its aqueous
solution was carried out by placing poly(Am-co-AMPS)
hydrogels, which are placed in 25 ml aqueous solutions of
dye having different strengths (25–200 mg/Lt) and
allowed to reach equilibrium for 5–6 days at room tem-
perature. After the stipulated period, the concentration of
the dye remaining in the solution was determined spec-
trometrically by using UV spectrophotometer (Parkin
Elmer USA Lambda 25). Aqueous solution of methyl
violet and fuchsine exhibited the maximum absorption
peak at about 585 and 549 nm, respectively. The equili-
brium concentration of dye molecules were then deter-
mined from the calibration curve already obtained with
the solutions of known concentration of the dye.
Morphological studies
Optical microscopic studies: The bulk or cross-sectional
morphology of the swollen gels was determined by using
optical microscope, KRUSS, A Kruss Optronic, Germany.
Figure 1. FTIR spectra of the dry hydrogels.
SEPARATION SCIENCE AND TECHNOLOGY 3
The dried gels were first swollen to equilibrium, and then,
thin strips of the gel sample were placed under microscope.
Cryo-SEM: The scanning electron micrographs of
the hydrogel samples in swollen condition were taken
by using cryogenic SEM apparatus, CARL ZEISS
EVO18, Special edition, Germany. Before up-taking
the image, the samples were cryo-fractured at −187°C
followed by gold coating with coating time of 2 minutes
in argon atmosphere at −150° to −160°C temperature.
Results and discussion
Spectroscopic studies
FTIR spectra of the hydrogels containing varying pro-
portions of monomers (AAm and AMPS) are shown in
Figure. 1.
A relatively sharp peak (m) is observed at 3445 cm−1
which is attributed to the N-H stretching of the amide
group. The band appearing at 1710 cm−1 is attributed to
carbonyl stretching vibration. A peak appearing at
1675 cm−1 may indicate the presence of amide moiety
on the polymer backbone.[15] The band at 2929 cm−1 is
assigned to the –CH2- stretching arising due to
polymerization.[16] The band at 1439 cm−1 represents
the C-N stretching vibration.[16] Moreover, the band at
1208 cm−1 is ascribed to the asymmetric SO2 stretching of
the AMPS segment in the polymer network.[17] Similar
observation has been made by Çavaş et al.[18] The band at
1032 cm−1 can be assigned to O-H stretching of the
sulfonic acid group. Two peaks at 1221 and 1233 cm−1
are also found to appear for sulfonic acid group. However,
4 R. BERA ET AL.
the shifting of these peaks in the higher wavelength region
may be ascribed to the ionization of the aforesaid groups
and the hydrogen bonding of the same with the neighbor-
ing amide moieties present in the polymer backbone.[18]
A weak peak is observed at 1626 cm−1 (amide II band),
and this possibly indicates the presence of –CONH
groups of AMPS. But as the AMPS percentage is low
compared to the other components, it is relatively weak
with respect to the other peaks. The peak at 1360 cm−1 is
attributed to antisymmetric stretch of SO2 group present
on the polymer backbone. The characteristic peak of
amide (1680 cm−1) has possibly been shifted to
1710 cm−1 in the present study due to the involvement
of hydrogen atoms of amide link in hydrogen bonding.[19]
The absence of peak in the range 1610–1640 cm−1 (for
conjugated C=C) and also in the range 3000–3100 cm−1
(for = C-H) indicates complete polymerization of the
constituent monomers. The above IR analysis indicates
the presence of all monomeric units in the cross-linked
network, and as such no functional groups are neither lost
nor generated during cross-linking.
Swelling studies
Swelling in water
The different poly (Am-co-AMPS) copolymer hydrogel
samples were allowed to swell in water at room tempera-
ture to reach equilibrium, and their different equilibrium
Figure 2. Variation of equilibrium swelling percentage of the (a) (Am-AMPS copolymer hydrogels with AMPS mole percentage at
constant crosslinker dose of 1 mole %, variation of swelling effficincy of the hydrogel AS10 with the (b) crosslinker concentration,
(c) initial total monomer concentration and (d) Variation of equilibrium swelling of the Poly acrylamide hydrogel (AS0) and
(Am-AMPS) copolymer hydrogels with pH of the medium.
swelling values were compared in respect of different
parameters as follows.
Variation with AMPS percent: On increasing the AMPS
proportions in the AAm/AMPS copolymer network, %
equilibrium swelling increases up to 10 mol% of the
AMPS content, and then, it falls off with further increase
in its content. The hydrogel with 10 mole% of AMPS shows
the maximum equilibrium swelling in water amongst the
different AAm/AMPS copolymer gels under study as
shown in Figure. 2(a) . Here, total monomer concentration
is fixed at 25% for all the hydrogels under study.
‘AMPS’ being an ionic monomer, its incorporation in
the cross-linked network of AAm is expected to increase
the hydrophilicity of the gel and its polarity as well,
resulting in an increase in the overall equilibrium swel-
ling. Moreover, there is a probability of formation of
intermolecular H-bonding between the two constituents
of the copolymer hydrogel (present in the neighboring
chain) through the C=O group of one AAm unit and the
H-atom of the –NH2 group of the other AAm unit result-
ing in a cage-like structure.[20–24] This type of inter-chain
H-bonding may sometimes act as pseudo-cross-links as
well. With the increase in AMPS content, the statistical
probability of formation of such intermolecular
H-bonding increases which creates extra space for accom-
modating water molecule and hence the swelling also
increases. This phenomenon, however, continues up to
10 mol% of its incorporation. On further increase in

AMPS content in the copolymer, a high accumulation of
strong ionic –SO3H group in the polymer network may be
expected to create ionic repulsion between the like
charges which tend to increase the distance between the
functional groups resulting in gradual decrease in H-bond
formation. The excess AMPS unit (beyond 10 mol%) may
thus decrease equilibrium swelling of the hydrogel, and it
may also be assumed that the steric hindrance effect of its
large giant molecular structure already formed may be a
deterrent for further H-bond formation and consequent
cage structure. Thus, the swelling decreases gradually with
increasing proportion of AMPS.
Variation with cross-link density: The hydrogels
under study do not dissolve in water due to cross-
linking, but it undergoes swelling in water or aqueous
solution. Equilibrium swelling of the polymer hydrogel
not only depends on the functional groups present in
the polymer network but also depends on the extent of
cross-linking between the polymer chains. The cross-
linked chains of the hydrogel matrix undergo relaxation
and make rooms or voids for solvent molecules, but the
chains cannot separate completely because they are
interconnected by cross-links. Thus with increase in
cross-link density as represented by mol% doses of
cross-linker, the relaxation of the polymer chains is
reduced causing a decrease in water absorption.[25] In
the synthesis of poly (AAm-co-AMPS) hydrogel, MBA
was used as a cross-linker. On increasing the doses of
cross-linker from 0.5 to 1 mol%, the equilibrium swel-
ling, however, decreases [Figure. 2(b)] possibly due to
the formation of a rigid tighter network with much less
free volume for accommodating the solvent which may
induce large force of shrinkage causing the gel to des-
well. Here, total monomer concentration is kept at 25%.
Variation with total monomer concentration: During
simultaneous polymerization and cross-linking reaction, a
cage-like structure may be assumed to be formed between
the polymer chains and the cross-links. The cross-linker
may also itself be involved in the formation of terpolymer.
When the initial total monomer concentration is compara-
tively high, the monomers and the cross-linker molecules
are very closely spaced. Hence, the size of the cage structure
becomes tiny, as the process of copolymerization and
cross-linking are possibly more predominant over the ter-
polymerization resulting in lower solvent entrapment
capacity.[26] This is reflected in case of the present gel also
where the equilibrium swelling value goes on decreasing
with increasing total monomer concentration from 20 to
100 mol/L during synthesis [Figure. 2(c)]. The hydrogels
with 20% AMPS have been developed using different total
monomer concentration, and the impact of this has been
studied on the equilibrium swelling percentage of the gels
in pH 7 and 25°C.
SEPARATION SCIENCE AND TECHNOLOGY 5
Variation of swelling in different pH solutions
To determine the pH sensitivity of the poly(AAm-co-
AMPS) hydrogels, the dried hydrogel samples were
allowed to swell to equilibrium in buffer solutions hav-
ing different pH at room temperature (25°C).
Equilibrium swelling of poly (AAm) hydrogel is inde-
pendent of pH of the swelling medium. On the other
hand, equilibrium swelling percentages of all poly
(AAm-co-AMPS) hydrogels were found to be strongly
dependent on the pH of the medium as revealed in
Figure. 2(d). Here, total monomer concentration is kept
at 25% during synthesis.
Equilibrium swelling percentages (%) of all the copo-
lymer hydrogels were found to increase first with the
increase in pH up to 7. Subsequently, this underwent a
decrease on further increase in pH of the medium. The
hydrogels were observed to swell to its maximum at pH
6.5 for all the hydrogels irrespective of compositions.
AMPS (having–SO3H groups) introduced in polymer
backbone ionizes quite easily even in neutral pH forming
–SO3− (sulfonate) ions. These sulfonate ions allure the
polar water molecules to enter into the cross-linked net-
work. The cage structure formed by the intermolecular
H-bonding between the carbonyl group of the amide
functionality and the acid functionality of the AMPS
unit of the neighboring chain may lead to structures
which can hold large amount of water molecules.[27]
Ionization of the –SO3H group is arrested in acidic
medium (pH < 7) as the medium already contains excess
H+ ions. Even the amide groups may undergo protona-
tion in acidic medium which prevents the formation of
the desired H-bonding responsible for accommodating
water molecules and thus may be responsible for
decrease in equilibrium swelling. In basic medium, ioni-
zation of the acid group increases with the formation of
large amount of –SO3− ions which repel each other
resulting in disruption of cage structure and decrease
in swelling. In an alkaline medium, the amide group also
is more reluctant to release its active amino hydrogen for
the necessary H-bond formation.
Swelling studies in different salt solutions
Variation with salt concentration: Swelling ability of the
AAm/AMPS copolymer hydrogel samples has been stu-
died using different concentrations of NaCl in swelling
media, that is, saline solutions [Figure. 3(a]. Equilibrium
swelling percentage of all the hydrogels in salt solutions is
found to be lower compared to that observed in pure
water. This can be explained by the fact that the swelling
of polyelectrolyte hydrogels is mainly due to the electro-
static interactions among the charge centers present on
the polymer chain, and hence, the extent of swelling is
influenced by any change in physical parameters, such as
6 R. BERA ET AL.
Figure 3. Variation of equilibrium swelling of the Poly acrylamide hydrogel (AS0) and (Am-AMPS) copolymer hydrogels with (a) salt
(sodium chloride) concentration, (b) size of the cations in the salt, (c) charge of the cations in the salt.
pH, ionic strength and type of counter-ions present in the
swelling medium which may alter these electrostatic
interactions.[28] This, however, occurs at very high pH
when concentration of sulfate ions is too large. On the
other hand, at lower pH range even in alkaline region, the
reverse situation occurs as the same anion exerts an
attractive or pulling force on the neighboring water mole-
cules. The increase in concentration of counter-ions in the
salt solution results in decrease in the osmotic swelling
pressure. This is responsible for the observed decrease in
swelling of the hydrogel samples.
Variation with salts of different cationic radius:
Swelling of the hydrogel samples has been carried out in
different salt solutions (LiCl, NaCl and KCl) having dif-
ferent cation sizes, but the salt concentration remaining
same in all cases [Figure. 3(b)]. Hydrogels swell little more
in NaCl solution compared to LiCl solution, but in case of
KCl solution it decreases though to a little extent. The
changes in swelling, however, vary marginally. Hence, the
sizes of the cations have little effects on the equilibrium
swelling of the AAm/AMPS hydrogel.
Variation with salts of different cationic charge:
Investigation of the influence of cationic charges of the
salt on the swelling ability of the present gel system has
been performed by measuring swelling efficiencies in
NaCl, CaCl2 and AlCl3 solutions [Figure. 3(c)]. Swelling
of poly (AAm) gel (sample AS0) is independent of the
cationic charges of the salts present in the swelling med-
ium. But swelling of all the poly (AAm-co-AMPS) hydro-
gels is strongly dependent on it. This dependency
increases with the increase of AMPS content in the poly-
mer network. The salts containing monovalent metal ions
give the most efficient swelling medium followed by diva-
lent and trivalent metal ions, respectively. Thus, the swel-
ling efficiency decreases in the order Na+ > Ca2+ > Al3+. It
is probably due to increase in ionic charge, that there is an
increase in ionic repulsion between the like charges which
hardly allows any entry of the solvent molecules contain-
ing similar charges into the cross-linked network.[29]
Deswelling studies
Poly (AAm-co-AMPS) hydrogels were allowed to swell
in distilled water (pH 6.5), and subsequently dropped
in the buffer solution of pH 4 when the hydrogels
started to deswell [Figure. 4 (a)].
This is due to protonation (or reverse ionization) of the
AMPS unit in relatively more acidic solution which
already has high H+ ion concentration. The decrease in
water content retained by the hydrogels was more or less
similar for all the hydrogels, though, equilibrium swelling
percentage (%) of the hydrogels was found to increase
with the AMPS content in the cross-linked network.

Figure 4. (a) Deswelling kinetics study in pH 4 medium and
(b) swelling-deswelling cycles (up to 2) of the (Am-Amps) based
hydrogels.
A reversible swelling–deswelling experiment (up to 2
cycles) had been performed to inspect the extent of ability
of recovering and repeated adsorption ability of the gels
[Figure. 4(b)]. The experiment showed that the ability to
recover is of higher order (almost 92.3%) for the gel with
15 mole percent of AMPS among the various gels under
this study. The hydrogel AS15 also shows fast response
time (almost half the time that is required for AS 2) in
respect to swelling–deswelling phenomenon. This may
encourage the reusability of such gel in water detoxifica-
tion in an economic manner (Table 2).
Separation of organic dyes
All the poly (AAm-co-AMPS) copolymer hydrogels were
found to be able in separating dyes from its aqueous
solution quite efficiently. The percentage of the basic
SEPARATION SCIENCE AND TECHNOLOGY 7
dye (methyl violet and fuchsine under study) removal of
the gel varied from 80 to 98% (Figure. 5). All the hydro-
gels contain ionized –SO3H groups that could easily inter-
act with the cationic groups of the basic dye. Other types
of interaction such as hydrogen bonding and hydropho-
bic interaction might have also played role in retaining the
dye molecules within the gel network.[30] Hydrogen
bonding might be expected to occur with the amine N
atom of dye and –SO3H group of the gel after its ioniza-
tion. The efficiency of separation was more prominent in
basic medium where almost 99% of dye removal became
possible with the hydrogels under study.
Effect of AMPS content
The virgin poly (AAm) gel can absorb only about
30–40% dye as shown by AS0 in Figure. 5(a). The
removal efficiency increases with the increase in
AMPS content and reaches equilibrium at 20% of the
AMPS content in copolymer. At this point, the dye
removal efficiency is about 95%. With the incorpora-
tion of anionic moieties in the polymer network, the
attraction for the cationic dye molecules increases and
so it absorbs more dye molecules. So hydrogel AS20
(with 20 mol% AMPS) has been used for further dye
separation experiments.
Effect of dosage of the hydrogel
The hydrogel dosage was varied from 0.25 to 5 g/Lt in
the dye solution. It is apparent from the Figure. 5(b)
that the dye removal efficiency increased with the
hydrogel concentration and reached 95% of its effi-
ciency at 4 g/Lt for both the dyes. This can possibly
be attributed to increase in surface area of contact with
the hydrogel and consequent increase in the capacity of
adsorption. Thus, for further experiments with dye
removal, the hydrogel dosage was kept at 4 g/Lt.
Effect of dye concentration
The effect of feed dye concentration on the net dye
removal capacity of the hydrogel has been investigated
within the feed concentration range of 25 to 400 mg/Lt
and has been shown in Figure. 5(c) for both the dyes
fuchsine and methyl violet, respectively. It is apparent
from the figure that the adsorption of dye molecules is
not very much affected by the feed dye concentration in
the range under studies. At higher dye concentration,
the dye adsorption slightly decreases.
Effect of contact time
Figure 5(d) shows the variations in percent dye
removed as a function of exposure time in contact
with gel. The trend is more or less the same for both
the dyes. Initially, the rate of dye removal is very high.
8 R. BERA ET AL.

Figure 5. Variation of dye removal efficiencies as function of (a) AMPS content in the hydrogel, (b) hydrogel feed concentration in
the dye solution, (c) dye concentration in aqueous solution, (d) time of contact of the gel in the dye solution, (e) pH of the dye
solution and (f) digital camera image of contact of the gel in the dye solution, (e) pH of the dye solution and (f) digital camera image
of after and before dye separation.

With time the rate slows down and finally reaches
equilibrium within 120 hours. So for, the subsequent
relevant experiments with dye removal duration of 120
hours have been stipulated for the maximum dye
adsorption of the gel. Initially, all the functional groups
of hydrogels of particular composition are available for
interacting with dye molecules, leading to a high initial
rate of dye removal. Later on the dye molecules have to
compete with each other to enter into the hydrogel
network, and the process becomes gradually slow.
Effect of pH of the dye solution
The effect of pH on the dye adsorption capacity of the
various hydrogels was examined by preparing the dye
solution in specific buffer solution having pH of 4, 7
and 9.1 keeping the dye concentration fixed at 100 mg/
Lt at room temperature. Figure 5(e) depicts that within
the pH range under study the variation of dye adsorp-
tion was marginal for both the dyes in all the hydrogels.
Lower dye adsorption at low pH is probably due to
protonation of the –SO3H groups.
Regeneration of the hydrogel and the dye
The dye-loaded hydrogel samples after equilibrium
absorption were immersed in aqueous solution of dif-
ferent pH, in methanol and in acetone, respectively, to
regenerate the hydrogels. The experiments were carried
out in a manner similar to that of dye removal
 SEPARATION SCIENCE AND TECHNOLOGY 9

experiments. There was no desorption observed in aqu-
eous solutions of pH 7 and 9, about 30–40% deso-
rption, however, occurred in buffer medium of pH 4.
Desorption was quite good in methanol and in acetone
solvent. It was about 45–50% in methanol and 50–60%
in acetone. The experimental results can be cited as an
evidence for the presence of electrostatic interaction
between the dye molecules and the hydrogel network.
The dyes desorbed in methanol and acetone could be
recovered directly after evaporating solvents.
It is quite apparent from Table 3 that the pseudo-
second-order kinetic model fitted better than that of the
pseudo-first-order model. The correlation coefficients
(R2) obtained from pseudo-second-order kinetic model
were higher than that of first-order model. The theoretical
qe values obtained from the pseudo-second-order kinetic
model were also closer to the experimental values. Hence,
it may be concluded that the pseudo-second-order kinetic
model was suitable for the adsorption of the dye by the
poly (AAm-co-AMPS) hydrogels under study.

Adsorption kinetics Adsorption isotherm

A representative image [Figure. 5(f)] shows the extent
of adsorption of dye (fuchsine) using AS20. Initially,
the rate of adsorption is very high, and then, the rate
falls with time until it reaches equilibrium adsorption.
The dye adsorption values at different time were fitted
into pseudo-first-order and pseudo-second-order
kinetic model in order to have better understanding
of the adsorption mechanism.
Pseudo-first-order kinetics. Lagergren pseudo-first-
order kinetic equation is given as follows[31]:
lnðqe  qt Þ ¼ lnqe  k1 t
Here, qe and qt are the dye adsorption (mg/g) at
equilibrium and at time t, respectively. k1 is the first-
order rate constants (Hr−1). The qe and k1 were obtained
from the intercept and slope of the linear plot of ln (qe-qt)
against t, respectively. The results along with the correla-
tion coefficients are given in Table 3.
Pseudo-second-order kinetics. According to McKay
and Ho, the pseudo-second-order kinetic equation is as
follows[31]:
 coefficient R2 values are illustrated in Table 4
t= ¼ 1 t
qt ðk2 q2e Þ þ =qe (4)
Here, k2 is the second-order adsorption rate constant
(g mg−1 Hr−1). The slopes and intercepts of the plot t/qt
against t give the values of k2 and qe, respectively.
In order to understand the interaction between adsorbent
and adsorbate, the dye adsorption values at different feed
dye concentrations were fitted to two most extensively
used equilibrium adsorption isotherm models namely
Freundlich and Langmuir equations.[32] Both the models
are suitable for adsorption on heterogeneous surfaces.
Freundlich Isotherm. The empirical equation is
given by Eq. (7).
1=
qe ¼ Kf  Ce n (5)
(3) where qe is the amount of dye adsorbed (mg/g), Ce is
the adsorbate equilibrium concentration (mg/Lt), Kf
(mg/g) and n (intensity of adsorption) are the
Freundlich constants which signify the nature of the
isotherm.[33] The constant values were calculated by
taking the logarithm of the above equation.
1
lnqe ¼ lnKf þ lnCe (6)
n
Then, lnqe was plotted against lnCe to get the
straight line. The constants Kf, n and the regression
Langmuir Isotherm. The equation for Langmuir
isotherm is given as
Ce= ¼ 1= þ Ce=
qe bq0 q0 (7)

Table 3. Calculated constant values of the dye adsorption kinetics.

Pseudo-first-order kinetics Pseudo-second-order kinetics
Hydrogel R2 K1(h–1) qe (mg/g) R2 K2 (g/mg h–1) qe(mg/g)
AS10 0.99045 0.0365 221.8 0.99492 1.1614 293.3
AS20 0.98371 0.03384 213.5 0.99589 0.8543 295.9

Table 4. Calculated constant values of the dye adsorption isotherms of the hydrogels.
Freundlich Langmuir
Hydrogel R2 K n R2 b (1 /mg) q0 (mg/g)
AS10 0.9562 162.6 21.3 0.9993 0.2171 213.68
AS20 0.9892 173.8 13.7 0.9997 0.1649 261.78
AS30 0.8377 233.2 50.5 0.99987 0.4987 261.78
10 R. BERA ET AL.

Figure 6. Hypothetical models explaining the probable phenomena occurred during dye adsorption.

where q0 (mg/g) and b (1/mg) are the Langmuir con-
stants which are related to the adsorption capacity and the
energy of adsorption, respectively.[34] The constant values
were calculated by plotting Ce/qe versus Ce, and the con-
stants along with the R2 values were given in Table 4.
The linear fitting of the isotherms were carried out by
Origin-8 software. It is apparent from the table that the
correlation coefficients R2 values for Langmuir isotherms
are higher than that of Freundlich isotherm. So Langmuir
model is the best-fit model for the adsorption of methyl
violet dye onto the AAm-co-AMPS hydrogel in the con-
ditions under studies.
The dye adsorption phenomenon has been tried to
explain with the help of few hypothetical models as

Figure 7. Optical microscopic images of the (Am-AMPS) copolymer hydrogels (a) AS2, (b) AS5, (c) AS10 and (d) AS15.
 SEPARATION SCIENCE AND TECHNOLOGY 11

shown in the Figure. 6. The models are drawn using 3d

MAX 2013 and compiled using Adobe photoshop CS6.
High affinity of AMPS block results in entrapment of the
cationic dye molecules in the inner mesh area. Similar
explanation has also been given by E. S. Dragan in his
review.[35] This results in contraction of the cages, which
may lead to better entrapment of the dye molecules. The
phenomenon concluded here is supposed to occur during
dye adsorption experiment.

Morphological studies
Optical microscopic studies
Figure 7 shows the microscopic porous images of cross-
sectional structure of the various poly (AAm-co-AMPS)
hydrogels in swollen condition in an increasing order of
AMPS from a-d.
A gradual increase in cell sizes was observed with the
increase in proportions of AMPS from 2 to 15%
(Figure. 7a–d). It was also attended with changes in
shapes as the almost tiny circular cells gradually became
irregular and a distribution of shapes was achieved, as
the AMPS content increased. The Figure. 7(c) looks the
most blurred one as the cells are mostly filled as
expected from our early swelling studies where we
find that the hydrogel with 10% of AMPS shows max-
imum swelling.

Cryo-SEM studies
Figure 8 shows the cross-sectional views of the internal
structures of the cryo-fractured hydrogel samples. The
hydrogels exhibit a discontinuous morphology.
The distribution and disposition of the cells in these
two representative samples of hydrogels containing 10
mol% of AMPS [Figure. 8(a)] and 15 mol% of AMPS
[Figure. 8(b)] were quite supportive to our earlier
observations on swelling studies. The cells in AS10
were deep rooted, more voluminous and sometimes
appeared to be internally communicated through open-
ings in cell walls. An approximate uniformity in cell
sizes is prevalent in AS10 while a wide distribution in
sizes is observed with AS15 while there is a significant
number of a small cell in AS15.
Conclusions
Copolymer hydrogels of poly (AAm-co-AMPS) were
prepared by using various AAm /AMPS ratios. These
hydrogels show pH and ionic strength-dependent swel-
ling and can be used in dye removal vehicles efficiently.
All the copolymer hydrogels absorb huge amount of
water, and so they may find use in water absorption.
Hydrogel with 10 mol% of AMPS swells to the
Figure 8. Cryo SEM images of the (Am-AMPS) copolymer hydro-
gels (a) AS10, (b) AS15.
maximum extent among the various poly (AAm-co-
AMPS) hydrogels irrespective of pH. All the hydrogels
absorb maximum (to different quantum) in around
neutral solution (~pH 7) and then falls on either side
of the entire range of pH. The hydrogels can remove
dyes efficiently irrespective of the dye concentration
and pH of the medium. It follows the pseudo-second-
order adsorption kinetics and Langmuir adsorption
isotherm during dye adsorption within the range
under studies. Hydrogels with higher AMPS percentage
show better recoverability and better performance dur-
ing repeated swelling experiments. Optical microscopic
pictures and SEM images clearly shows the porous
cross-sectional structure of the gels.
Abbreviations
AAm acrylamide
AMPS 2-acrylamido-2-methylpropane sulfonic acid
MBA N,N’-methylenebisacrylamide
12 R. BERA ET AL.
Acknowledgements
The authors extend their gratitude to Prof. D. Chattopadhyay
for assistance in scanning electron microscopic study of the
samples.
Funding
The authors gratefully acknowledge the University of
Calcutta, Kolkata, for providing research facilities and UGC,
India,for the fundings.
References
[1]. Ahmad, A.; Mohd-Setapar, S.H.; Chuo, S.C.; Khatoon,
A.; Wani, W.A.; Kumar, R.; Rafatullah, M. (2015)
Recent advances in new generation dye removal tech-
nologies: novel search for approaches to reprocess was-
tewater. RSC Advances, 5: 30801–30818.
[2]. Wang, X.C.; Zhang, C.; Ma, X.; Luo, L. (2015) Water
Cycle Management: A New Paradigm of Wastewater
Reuse and Safety Control. Springer: Berlin.
[3]. Sharma, S.K. (2015) Green Chemistry for Dyes
Removal from Waste Water: Research Trends and
Applications. John Wiley & Sons.
[4]. Kasgoz, H.; Durmus, A. (2008) Dye removal by a novel
hydrogel-clay nanocomposite with enhanced swelling
properties. Polymers for Advanced Technologies, 19:
838–845.
[5]. Karadag, E.; Saraydin, D.; Cetinkaya, S.; Guven, O.
(1996) In vitro swelling studies and preliminary bio-
compatibility evaluation of acrylamide-based hydro-
gels. Biomaterials, 17(1): 67–70.
[6]. Isik, B.J. (2004) Swelling behavior and determination of
diffusion characteristics of acrylamide-acrylic acid
hydrogel. Journal of Applied Polymer Science, 91:
1289–1293.
[7]. Bajpai, S.K. (2001) Swelling–deswelling behavior of
poly(acrylamide-co-maleic acid) hydrogels. Journal of
Applied Polymer Science, 80: 2782–2789.
[8]. Saraydin, D.; Karadag, E.; Güven, O. Polym. (1994)
Acrylamide/maleic acid hydrogels. Polymers for
Advanced Technologies, 6: 719–726.
[9]. Qiu, Y.; Park, K. (2001) Environment-sensitive hydro-
gels for drug delivery. Advanced Drug Delivery Reviews,
53: 321–339.
[10]. Çaykara, T.; Doǧmuş, M.; Kantoǧlu, O. (2004)
Network structure and swelling–shrinking behaviors
of pH-sensitive poly(acrylamide-co-itaconic acid)
hydrogels. Journal of Polymer Science Part B: Polymer
Physics, 42: 2586–2594.
[11]. Li, W.; Zhao, H.; Teasdale, P.R.; John, R.; Zhang, S.
(2002) Synthesis and characterisation of a polyacryla-
mide–polyacrylic acid copolymer hydrogel for environ-
mental analysis of Cu and Cd. Reactive & Functional
Polymers, 52: 31–41.
[12]. Cavus, S. (2010) Poly(methacrylamide-co-2-acryla-
mido-2-methyl-1-propanesulfonic acid) hydrogels:
Investigation of pH- and temperature-dependent swel-
ling characteristics and their characterization. Journal
of Polymer Science: Part B: Polymer Physics, 48: 2497–
2508.
[13]. Travas-Sejdic, J.; Easteal, A.J. (2000) Equilibrium swel-
ling of poly(AAm-co-AMPS) gels in surfactant solu-
tions. Polymer, 41: 7451–7458.
[14]. Durmaz, S.; Okay, O. (2000) Acrylamide/2-acrylamido-
2-methylpropane sulfonic acid sodium salt-based
hydrogels: synthesis and characterization. Polymer, 41:
3693–3704.
[15]. Agnihotri, S.A.; Aminabhavi, T.M. (2006) Novel inter-
penetrating network chitosan-poly (ethylene oxide-g-
acrylamide) hydrogel microspheres for the controlled
release of capecitabine. International Journal of
Pharmaceutics, 324: 103–115.
[16]. Zhu, L.; Zhang, L.; Tang, Y.; Kou, X. (2014) Synthesis of
sodium alginate graft poly (acrylic acid-co-2-acryla-
mido-2-methyl-1-propane sulfonic acid)/attapulgite
hydrogel composite and the study of its adsorption.
Polymer-Plastics Technology and Engineering, 53: 74–79.
[17]. Cavus, S.; Gurdag, G. (2009) Noncompetitive removal
of heavy metal ions from aqueous solutions by poly [2-
(acrylamido)-2-methyl-1-propanesulfonic acid-co-ita-
conic acid] hydrogel. Industrial & Engineering
Chemistry Research, 48: 2652–2658.
[18]. Çavuş, S.; Gürdağ, G. (2008) Competitive heavy metal
removal by poly (2-acrylamido-2-methyl-1-propane
sulfonic acid-co-itaconic acid). Polymers for Advanced
Technologies, 19: 1209–1217.
[19]. Hirashima, Y.; Sato, H.; Suzuki, A. (2005) ATR-FTIR
Spectroscopic Study on Hydrogen Bonding of Poly(N-
isopropylacrylamide-co-sodium acrylate) Gel.
Macromolecules, 38: 9280–9286.
[20]. Khutoryanskaya, O.V.; Morrison, P.W.J.; Seilkhanov, S.
K.; Mussin, M.N.; Ozhmukhametova, E.K.;
Rakhypbekov, T.K.; Khutoryanskiy, V.V. (2014)
Hydrogen-bonded complexes and blends of poly
(acrylic acid) and methylcellulose: nanoparticles and
mucoadhesive films for ocular delivery of riboflavin.
Macromolecular Bioscience, 14: 225–234.
[21]. Lejardia, A.; Hernándeza, R.; Criadoa, M.; Santosc, J.I.;
Etxeberriad, A.; Sarasuab, J.R.; Mijangos, C. (2014)
Novel hydrogels of chitosan and poly(vinyl alcohol)-
g-glycolic acid copolymer with enhanced rheological
properties. Carbohydrate Polymers, 103: 267–273.
[22]. Hu, X.; Feng, L.; Xie, A.; Wei, W.; Wang, S.; Zhang, J.;
Dong, W. (2014) Synthesis and characterization of a
novel hydrogel: salecan/polyacrylamide semi-IPN
hydrogel with a desirable pore structure. Journal of
Materials Chemistry B, 2: 3646.
[23]. Scherzinger, C.; Schwarz, A.; Bardow, A.; Leonhard, K.;
Richtering, W. (2014) Cononsolvency of poly-N-iso-
propyl acrylamide (PNIPAM): Microgels versus linear
chains and macrogels. Current Opinion in Colloid &
Interface Science, 19 (2): 84–94.
[24]. Shirakura, T.; Kelson, T.J.; Ray, A.; Malyarenko, A.E.;
Kopelman, R. (2014) Hydrogel Nanoparticles with
Thermally Controlled Drug Release. ACS Macro
Letters, 3: 602−606.
[25]. Pourjavadi, A.; Ghasemzadeh, H.; Mojahedi, F. (2009)
Swelling properties of CMC-g-poly (AAm-co-AMPS)
superabsorbent hydrogel. Journal of Applied Polymer
Science; 113 (6): 3442–3449.

[26]. Yıldız, B.; Işık, B.; Kış, M. (2001) Synthesis of thermo-
responsive N-isopropolylacrylamide-N-hydroxymethy-
lacrylamide hydrogels by redox polymerization.
Polymer, 42 (6): 2521–2529.
[27]. Dubey, S.; Bajpai, S.K. (2006) Poly(methacrylamide-co-
acrylic acid) hydrogels for gastrointestinal delivery of
theophylline: Part – I: swelling characterization.
Journal of Applied Polymer Science, 101: 2995–3008.
[28]. Ritger, P.L.; Peppas, N.A. (1987) A simple equation for
description of solute release I. Fickian and non-Fickian
release from non-swellable devices in the form of slabs,
spheres, cylinders or discs. Journal of Controlled
Release, 5: 23–36.
[29]. Kaith, B.S.; Jindal, R.; Mittal, H. (2010) Superabsorbent
hydrogels from poly (acrylamide-co-acrylonitrile) grafted
Gum ghatti with salt, pH and temperature responsive
properties. Der Chemica Sinica, 1 (2): 92–103.
[30]. Karadağ, E.; Saraydin, D.; Güven, O. (1997) Cationic dye
adsorption by acrylamide/itaconic acid hydrogels in
SEPARATION SCIENCE AND TECHNOLOGY 13
aqueous solutions. Polymers for Advanced Technologies, 8:
574–578.
[31]. McKay, G.; Ho, Y.S. (1999) Pseudo-second order model
for sorption processes. Process Biochemistry, 34: 451–465.
[32]. Aydin, H.; Baysal, G. (2006) Adsorption of acid dyes in
aqueous solutions by shells of bittim (Pistacia khinjuk
Stocks). Desalination, 196: 248–259.
[33]. Arami, M.; Limaee, N.Y.; Mahmoodia, N.M.; Tabrizi,
N.S. (2006) Equilibrium and kinetics studies for the
adsorption of direct and acid dyes from aqueous solu-
tion by soy meal hull. The Journal of Hazardous
Materials, 135 (1): 171–179.
[34]. Baskaralingam, P.; Pulikesi, M.; Ramamurthi, V.;
Sivanesan, S. (2006) Equilibrium
[35]. studies for the adsorption of acid dye onto modified hec-
torite. Journal of Hazardous Materials, 136 (3): 989–992.
[36]. Dragan, E.S. (2014). Design and applications of inter-
penetrating polymer network hydrogels. A review.
Chemical Engineering Journal, 243, 572–590.