J Polym Res (2009) 16:6372
DOI 10.1007/s10965-008-9203-5
Radiation synthesis of kappa-carrageenan/acrylamide
graft copolymers as superabsorbents
and their possible applications
H. L. Abd El-Mohdy & H. A. Abd El-Rehim
Received: 25 December 2007 / Accepted: 18 April 2008 / Published online: 24 May 2008
# Springer Science + Business Media B.V. 2008
Abstract Kappa-carrageenan (C) was modified via graft
copolymerization of acrylamide (AAm) using -irradiation
and followed by alkaline hydrolysis to achieve a novel
superabsorbent hydrogel. The effect of grafting variables
and alkaline hydrolysis conditions such as C/AAm
compositions and irradiation doses, NaOH concentration,
hydrolysis time and temperature were systematically opti-
mized to achieve a hydrogel with swelling capacity as high
as possible. Swelling properties and FT-IR of untreated C-
g-PAAm and hydrolyzed C-g-PAAm (H-C-g-PAAm)
were determined. The swelling capacity of hydrolyzed
C-g-PAAm was about 10 times in distilled water and three
times in NaCl solution higher than that for C-g-PAAm.
The swelling of superabsorbing hydrogels was examined in
buffer solutions. The swelling capacity of hydrogels was
also measured in various salt solutions (LiCl, NaCl, KCl,
CaCl2, and FeCl3). Results indicated that the swelling ratios
decreased with an increase in the ion radius, valence and
ionic strength of the salt solutions. Due to their high
swelling ability in salt solutions, the hydrogels may be
referred to as anti-salt superabsorbent polymers. Thus, the
salinity of water treated with H-C-g-PAAm hydrogels was
determined. It was found that the H-C-g-PAAm hydrogels
have a capability to absorb and retain the fresh water from
the saline solution. The results obtained suggested the
possible used of such prepared superabsorbent in agricul-
tural purposes as a material for sodic soil remediation.
H. L. Abd El-Mohdy (*) : H. A. Abd El-Rehim
Polymer Chemistry Department,
National Center for Radiation Research and Technology,
3 Ahmad El-Zomor Street, P. O. Box No. 29,
Nasr City, Cairo, Egypt
e-mail: hatem_lotfy@yahoo.com
Keywords Kappa-carrageenan . Hydrogels .
Superabsorbent . Irradiation . Graft . Swelling . Salinity
Introduction
Superabsorbent hydrogels (SAPs) are three-dimensional
hydrophilic crosslinked networks, which are able to absorb
and retain many times their weight of water, saline or
biological fluids, without dissolution [12]. Synthesis and
characterization of these attractive materials have received
significant attention because of their excellent applications
in many fields. Hydrogels specially are used in disposable
diapers, hygienic napkins, and agricultural applications
and in medicine as drug delivery carriers[25]. Nowadays,
the worldwide production of synthetic SAPs is more than
one million tons per year and this may cases damaged to
environment. Natural-based superabsorbent hydrogels
have attracted much interest from the viewpoint of
improving the tissue tolerance of synthetic polymers and
the mechanical properties of natural polymers. Because of
their bio-compatibility, biodegradability and non-toxicity,
polysaccharides are the main part of the natural-based
superabsorbent hydrogels.
Free radical graft copolymerization of vinyl monomers
onto poly-saccharide back-bones followed by crosslinking
of their chains is a well-known method for the synthesis of
these biopolymer-based networks [67]. Since the devel-
opment of the first superabsorbent hydrogel, the hydrolyzed
starch-g-polyacrylonitrile, in the late 1960s, monomers
such as acrylic acid and acrylamide have been graft
copolymerized onto polysaccharides such as starch, cellu-
lose and their derivatives [67] to prepare superabsorbent
hydrogels. Carrageenans are relatively new polysaccharides
in the synthesis of natural-based superabsorbent polymers.
64 H.L. Abd El-Mohdy, H.A. Abd El-Rehim

O
These biopolymers are linear sulfate polysaccharides that are
obtained from certain species of red seaweeds [8]. The H2C C C NH2
H
presence of hydrophilic sulfate groups with high ionization
tendency and less sensitivity to salt solution was the main Acrylamide
concept for synthesis of carrageenan-based superabsorbent Chemical Formula: C3H5NO

hydrogels. Recently, kappa-carrageenan was found to en-

OSO3 O
hance the properties of synthetic hydrogels by incorporation OH
into the water-soluble polymer systems such as polyethylene O
O
oxide and poly N-vinyl pyrrolidone (PVP) etc [913]. O O
Hydrogels likely reduce the effects of salts in the soil OH
matrix, even though they limit water carrying capacity. Kappa-carrageenan OH
Salinity in soils affects plant growth by osmotic inhibition Chemical Formula: C14H23O12S-
of water, nutritional imbalance caused by excessive salts, Fig. 1 Chemical structures of kappa-carrageenan and acrylamide
and toxic effects by high concentrations of salts in the
soil. In one study, the incorporation of hydrogels into a
growing media containing various salt concentrations The samples were cooled and then irradiated at room
actually increased plant vitality. Under the control in the temperature by a 60Co- source.
experiments conducted by tomato and cucumber died in
pure sand with concentrations of salt less than 8,000 ppm Gel fraction
and lettuce died at salt concentrations of less than
4,000 ppm. When the hydrogel was incorporated into the To extract the insoluble parts of the hydrogels (i.e., the
sand mix all three species were able to live with salt gelled part), the prepared hydrogels were soaked in water
concentrations of 32,000 ppm and actually performed better for 48 h at 100C. Then, they were taken out and washed
than in pure sand substrates with no salt. Although the with hot water to remove the soluble part, dried, and
plants were stunted, they generally had increased pigments, weighed. The gel percent in the hydrogel was determined
photosynthesis activity, amino acids, proline, and protein from Eq. 1:
contents [14].
In this work, superabsorbent hydrogel of kappa-carrageenan- Gel% We=Wg
100 1
graft-polyacrylamide (C-g-PAAm) were synthesized by a where We and Wg are dry hydrogel weights after and
simultaneous irradiation technique using -rays. The optimi- before extraction, respectively.
zation of synthetic conditions to achieve maximum swelling
(H-C-g-PAAm) was performed. The ability for such prepared Swelling measurement
superabsorbents to absorb the fresh water from the saline
solution was investigated. The dried hydrogels of known weights were immersed in
distilled water or saline solution at 25C until the swelling
equilibrium was reached (almost 24 h). The gel was
Experimental removed, blotted quickly with absorbent paper, and then
weighed. For accuracy, the experiment was repeated twice
Materials for each sample. The following equation was used to
determined water uptake:
Kappa-carrageenan purchased from Condinson Co., Denmark.
Swelling Ws  Wg=Wg 2
Acrylamide (Merck, Darmstadt, Germany) was used as
received. The chemical structures and formula of kappa- Where Ws and Wg are the weights of wet and dry gel,
carrageenan and acrylamide were shown in Fig. 1. The other respectively.
chemicals, such as solvents and inorganic salts, were reagent
grade and used without further purification. Alkaline hydrolysis

Preparation of the C/PAAm graft copolymers
Kappa-carrageenan were dissolved in distilled water at 80C
for 2 h. The hot C solution was mixed with AAm, and then
poured into a glass tube of diameter 15 mm. The final
concentrations in the mixture of C and AAm were 20%.
The graft copolymer (0.50 g) was saponified using 20.0 ml
of NaOH (0.53.5 N) in a two-neck flask fitted with a
mechanical stirrer and a reflux condenser. The hydrolysis
temperatures of 30100C; and hydrolysis times of 10
100 min were studied. The mixture was allowed to cool to
room temperature and neutralized to pH 8.0 by addition of
Radiation synthesis of -carrageenan/acrylamide graft copolymers
10 wt% aqueous acetic acid solution. Then the product was
poured into methanol (200 ml) to dewater for 10 h. The
hardened particles were filtered off, dried in an oven (50C,
5 h), and kept in a dry and cool place.
Swelling rate
In order to study the absorbency rate of the hydrogels,
certain amount of samples (0.5 g) was poured into numbers
of weighed tea bags and immersed in distilled water
(200 ml). At consecutive time intervals, the equilibrium
swelling capacity of the hydrogels was measured according
to the earlier mentioned method.
Measurement of hydrophilic groups
In some extent, RCOONa is a weak alkali, COONa
group amount in the hydrogel can be measured by titrating
with stronger acid HCl. A hydrogel sample (0.5 g) was
weighed and put into a NaCl saturation solution (to ensure
RCOONa ionizes completely [15], then drips HCl
standard solution into the sample solution slowly, and the
titration end point was judged by potentiometer. The molar
percentage of COONa in the sample was calculated by
following equation.
COONamol% CHCI
VHCI
 One gram of each hydrogel sample was soaked in 100 ml of

71 Wsample
100%
The COOH group in the composite can be neutralized
by NaOH and its amount can be measured by electrochem-
istry method. A sample (0.5 g) was immersed in overweight
NaOH solution for 24 h to allow COOH group transfer to
COONa group completely. The residual NaOH was
titrated by using HCl standard solution and the end point
of the neutralization reaction was judged by potentiometer.
The molar percentage of COOH in the sample was
calculated according to the Eq. 4.
COOHmol% CNaOH
VNaOH  CHCI
VHCI


71 Wsample
100%
It is difficult to directly measure the percentage of CONH2
group in the hydrogel, CONH2 group can be measured by
transferring CONH2 group to COONa group according to
the reaction 5. A sample (0.5 g) was put into an overweight
NaOH solution and was heated up to 95C for 4 h, then the
solution is boiled to ensure the following reaction takes place
and the NH3 was removed completely.
R  CONH2 NaOH95 C; 4h
! R  COONa NH3 "
65
The boiled solution was cooled and titrated with
standard HCl solution. Meanwhile, a blank test (without
heating 95C and boiling) was done. The molar percentage
of CONH2 group in the sample was calculated according
to the Eq. 6:
COOHmol%
CNaOH
VNaOH  CHCI
VHCI  Cblank
Vblank


71 Wsample
100%
6
FT-IR spectroscopy
The samples were powdered and mixed with KBr to make
pellets. Analysis by Infra Red Spectroscopy was carried out
by using Mattson 1000,Unicam, Cambridge, England in the
range from 4004,000 cm1
pH measurements
The pH of solutions was determined by using Jenway 3310
pH Meter.
Salinity assay
3
0.9% NaCl solution, the salinity of saline solutions were
detected by using Conductivity Meter, WTW, LF340,
Germany.
Results and discussion
Preparation of a new type of water superabsorbent (H-C-
g-PAAm) is performed by crosslinking graft copolymeriza-
tion of AAm onto C backbones followed by hydrolysis
with NaOH solution (H-C-g-PAAm). The effect of
grafting variables and alkaline hydrolysis conditions such
4 as C/AAm compositions and irradiation doses, NaOH
concentration, hydrolysis time and temperature were sys-
tematically optimized to achieve a hydrogel with swelling
capacity as high as possible.
Gel content
Gel content and crosslinking network density of prepared
polymer have a great influence on its swelling character.
There are many factors affecting the polymer gel content
among them, polymer compositions and irradiation doses.
The gel content of C/PAAm of different compositions
5 prepared at various irradiation doses was investigated and
66 H.L. Abd El-Mohdy, H.A. Abd El-Rehim

shown in Fig. (2). It is clear that the gel content of C-g-

PAAm hydrogel increases with increasing the amount of
AAm in the copolymer feed solutions as well as irradiation
dose. The maximum gel content obtained for pure PAAm
gels at different irradiation doses. PAAm is well known as a
crosslinked polymer by radiation. Consequently, as the
polyacrylamide increases in the graft copolymer, the gel
content increases.

Swelling of C-g-PAAm

The swelling of C-g-PAAm hydrogel of different compo-

sitions was investigated and shown in Fig. (3). It reveals
that the swelling ratio continuously decreases with increas-
ing the irradiation dose and acrylamide content in the graft
copolymer. The results can be explained by the fact that the
increasing of AAm content in the feed solution resulted in
dense crosslinked polyacrylamide chains in the hydrogel
network which decreases swelling and restricted the water
diffusion into prepared copolymers. The phenomena of gel
swelling has been the subject of numerous studies in
polymer physics. It has been demonstrated that minute
changes in external conditions such as temperature, solvent
composition, and ionic strength can induce drastic changes
in state of the swollen network [16]. In this connection, it is
an important to understand the osmotic and structural
changes of polymer gels induced by addition of some salts.
Therefore, the effect of NaCl solution on the swelling
behavior of C-g-PAAm hydrogels prepared by -irradiation
is investigated and shown in Fig. (4). In general, the swelling
of hydrogels in 0.9 wt. % NaCl solution is much lower than
that obtained in distilled water.
Fig. 3 Effect of various C/AAm compositions on the swelling of
C-g-PAAm hydrogel at different irradiation doses. Polymer conc.,
20% (wt/vol)
Hydrolysis of C-g-PAAm
Practically, most of acrylamide-based polymers are actually
partially hydrolyzed to introduce some carboxylic groups
into the chain. The presence of these charged units
improves water solubility and increase hydrodynamic
volume of the chain due to the mutual repulsion of the
negative charges [1719].
Concentration of NaOH
The alkaline hydrolysis of the graft copolymer, C-g-
PAAm, was carried out using different concentrations of
NaOH (0.53.5 N) and their swelling capacity was
determined. As shown in Fig. (5), swelling capacity is
increased with increasing the NaOH concentration, to reach

Fig. 2 Effect of various C/AAm compositions on the gel (%) of C- Fig. 4 Effect of various C/AAm compositions on the swelling of
g-PAAm hydrogel at different irradiation doses. Polymer conc., 20% C-g-PAAm hydrogel in 0.9% NaCl at different irradiation doses.
(wt/vol) Polymer conc., 20% (wt/vol)
Radiation synthesis of -carrageenan/acrylamide graft copolymers
Fig. 5 Influence of NaOH concentration on the swelling of H-C-g-
PAAm superabsorbent hydrogel. Polymer conc., 20% (wt/vol), polym.
Composition; 10:90 (C/AAm wt/wt), irradiation dose; 10 kGy.
Alkaline hydrolysis conditions: 80C and 60 min
a maximum at 3.0 N NaOH concentration thereafter, it
decreases with increasing NaOH concentration. Alkaline
degradation of the polysaccharide backbone is the reason
for the swelling decrease in highly concentrated alkaline
hydrolytic media [2021].
Temperature of hydrolysis
The relationship between the hydrolysis temperature of C-
g-PAAm and swelling capacity of H-C-g-PAM was
studied (Fig. 6). Swelling capacity is increased with
increasing the temperature, to reach a maximum at 80C
thereafter, it decreases as the temperature increases. By
increasing the hydrolysis temperature up to 80C, the
kinetics of alkaline hydrolysis increased which, in turn,
results in carboxylate anion increment and consequently,
Fig. 6 Influence of hydrolysis temperature on the swelling of H-C-
g-PAAm superabsorbent hydrogel. Polymer conc., 20% (wt/vol),
polym. composition; 10:90 (C/AAm wt/wt), irradiation dose;
10 kGy. Alkaline hydrolysis conditions: 60 min, 3 N
67
absorbency enhancement. Decreasing the swelling capacity
may be attributed to alkaline degradation of the C part of
the hydrogel over this temperature.
Hydrolysis time
In this series of experiments, swelling capacity of the final
hydrogel, H-C-g-PAAm, was studied as a function of the
hydrolysis time of C-g-PAAm (Fig. 7). Swelling capacity
is increased with increasing the time, to reach a maximum
at 60 min thereafter; it decreases as the time increases. By
increasing the hydrolysis time, the kinetics of alkaline
hydrolysis increased which, in turn, results in carboxylate
anion increment and consequently, absorbency enhance-
ment. Decreasing the swelling capacity may be attributed to
alkaline degradation of the C part of the hydrogel.
FT-IR spectroscopy
Infrared spectroscopy was carried out to confirm the chemical
structure of the prepared graft copolymers. Figure (8)
shows the FT-IR spectra of C, C-g-PAAm, and
H-C-g-PAAm. The bands observed at 842, 913, 1,080,
1,222, and 3,2003,400 cm1 can be attributed to D-
galactose-4-sulfate, 3,6-anhydro-D-galactose, glycosidic
linkage, ester sulfate stretching, and stretching of OH
groups of non-modified C, respectively (Fig. 8a). The
graft copolymer, C-g-PAAm, comprises a C-backbone
with side chains that carry carboxamide functional groups
that are evidenced by a new peak at 1,660 cm1 (Fig. 8b).
This peak attributed to C=O stretching in carboxamide
functional groups of PAAm. The stretching band of NH
overlapped with the OH stretching band of the C portion
of the copolymer. After alkaline hydrolysis, the new
Fig. 7 Influence of hydrolysis time on the swelling of H-C-g-PAAm
superabsorbent hydrogel. Polymer conc., 20% (wt/vol), polym.
composition; 10:90 (C/AAm wt/wt), irradiation dose; 10 kGy.
Alkaline hydrolysis conditions: 80C, 3 N
68 H.L. Abd El-Mohdy, H.A. Abd El-Rehim

Fig. 8 FT-IR spectra of a C, b C-g-PAAm, c H-C-g-PAAm

absorption modes at 1,459 and 1,557 cm1 can be attributed

to symmetric and asymmetric stretching modes of carboxyl-
ate groups, respectively (Fig. 8c) [22]. As shown in Fig. (8c),
after partially alkaline hydrolysis of the C-g-PAAm, some
of the amide groups are converted to carboxylate anions.

H-C-g-PAAm swelling behavior

The swelling capacity of both C-g-PAAm and H-C-g- Fig. 9 Swelling of various compositions of C-g-PAAm and H-C-g-
PAAm which prepared with optimum grafting and hydro- PAAm superabsorbent hydrogels in distilled water (a) and 0.9% NaCl
lysis conditions at different C/AAm compositions in solution (b). Polymer conc., 20% (wt/vol) irradiation dose; 10 kGy
distilled water and in 0.9% NaCl solution was investigated
and shown in Fig. (9). It is clear that the NaOH treated C- process according to the Eq. 5. Noticeable, owing to the
g-PAAm copolymers water absorbency is much higher than reaction equilibrium and other compounds in the solution,
that of untreated C-g-PAAm copolymers in distilled water under the condition of preparation, the conversion cannot
and in 0.9% NaCl solution. The maximum swelling value take place quantificationally. For example, when the con-
(950, 70 g/g in distilled water and 0.9% NaCl solution
respectively) was observed for H-C-g-PAAm copolymers
of C/AAm composition; (20/80 wt%). Improvement of
hydrogel water absorbency can be attributed to the
electrostatic repulsion of its network ionic charges. Increasing
of charged carboxylate groups in H-C-g-PAAm enhances its
affinity towards water; the higher the ionic charge in the
copolymer, the higher the water absorbency was obtained
[2324]. The formed carboxylic and charged carboxylate
groups which enhance the swelling of H-C-g-PAAm
superabsorbent hydrogels as a result of the partial hydrolysis
of acrylamide groups are shown in Scheme 1. The relation
between the molar percentage of CONH2, COONa and
COOH group and the amount of NaOH in the hydrolysis
reaction is shown in Table 1. It can be found that the molar
percentage of CONH2 group decreases and that of COOH
or COONa group increase with the increase of the amount
of NaOH in the hydrolysis reaction, i.e. CONH2 group is Scheme 1 Partial hydrolysis of amide groups at polyacrylamide
converted to COOH or COONa group in the hydrolysis chains
Radiation synthesis of -carrageenan/acrylamide graft copolymers 69

Table 1 Variation of the amount of hydrophilic groups with different different atomic radii, valences and ionic strengths. The
NaOH concentrations in hydrolysis for C-g-PAAm hydrogels under
C-g-PAAm and H-C-g-PAAm hydrogels belong to an
the conditions of 80C and 60 min
anionic type absorbent, thereby making it worthwhile to
NaOH concentration (N) Group amount (%) investigate the effect of counter ions (cations) and their
ionic strength on swelling behavior of the C-g-PAAm and
CO=NH2 COOH COONa
H-C-g-PAAm which have (SO42) and (SO42 and
0.5 60 5 10 COO) anionic groups, respectively. Therefore, the effect of
1.0 51 10 20 various salt solutions of different valences on the swelling
1.5 42 15 30 properties of gel is investigated.
2.0 31 20 40
2.5 22 25 50
Effect of valence of cations on H-C-g-PAAm swelling
3.0 18 31 58
3.5 14 36 64
The swelling behavior of H-C-g-PAAm hydrogels im-
Composition; 10:90 (C/AAm wt/wt) and irradiation dose; 10 kGy mersed in various salt solutions of different ionic valences
(Na+, Ca2+ and Fe3+) at various ionic strengths is shown in
centration of NaOH is 1, only 80% of CONH2 is conversed, Fig. (10). Under a given ionic strength, the swelling
instead of 100%. decreases as the ionic valence of the salt ions increases,
the minimum swelling capacity obtained when in trivalent
Swelling in various salt solutions ions (Fe3+) was used and maximum one observed when
monovalent ions (Na+) was used. Alkali metal ions can
It is an important to understand the osmotic and structural freely move all over the entire network. Addition of
changes of polymer gels induced by addition of salts have divalent or trivalent counter ions which leads to a volume

Fig. 10 Swelling capacity of the hydrogels, a C-g-PAAm and b H- Fig. 11 Swelling capacity of the hydrogels, a C-g-PAAm and b H-
C-g-PAAm, in various concentrations of different salt solutions. C-g-PAAm, in various univalent cation solutions. Polymer conc.,
Polymer conc., 20% (wt/vol), polym. composition; 20/80 (C/AAm 20% (wt/vol), polym. composition; 20/80 (C/AAm wt/wt), irradia-
wt/wt), irradiation dose; 10 kGy tion dose; 10 kGy
70
Fig. 12 Effect of pH on swelling capacity of H-C-g-PAAm
superabsorbent hydrogels. Polymer conc., 20% (wt/vol), polym.
composition; 10:90 (C/AAm wt/wt), irradiation dose; 10 kGy
transition in H-C-g-PAAm gels, governed by the inter-
actions between the polyion and the counter ions.
Alkaline earth-metal ions bind strongly with double
carboxylate groups, and its mobility through the polymer
network become limited. However, H-C-g-PAAm network
exhibits strong chelating ability with heavy metal ions (Fe3+),
and as a result, the ion mobility is restricted. It was reported
that the amount of gel water retained is affected by chemicals
or divalent cations present in the water. These cations
develop strong interactions with the polymer gels and are
able to displace water molecules trapped within the gel [25
27]. Even though monovalent cations such as Na+ can
replace water molecules, this effect is not as pronounced as
with the divalent counterparts. Furthermore, the process is
fully reversible by repeated soaking with distilled water.
Fig. 13 Swelling rate of C-g-PAAm and H-C-g-PAAm superab-
sorbent hydrogels. Polymer conc., 20% (wt/vol), polym. composition;
10:90 (C/AAm wt/wt), irradiation dose; 10 kGy
H.L. Abd El-Mohdy, H.A. Abd El-Rehim
Fig. 14 Salinity of various compositions of H-C-g-PAAm superab-
sorbent hydrogels. Polymer conc., 20% (wt/vol) irradiation dose;
10 kGy
Effect of ionic radius of cations on H-C-g-PAAm swelling
To investigate the salt-sensitivity of the C-g-PAAm and
H-C-g-PAAm, the equilibrium swelling was measured in
chloride salt solutions of monovalent cations, Li+, Na+, and
K+ with various ionic strengths (Fig. 11). The water
absorbency of the H-C-g-PAAm hydrogels decrease with
increasing ionic strengths. Also, the water absorbency of
the H-C-g-PAAm hydrogels increases with decreasing
atomic radius of monovalent cation solutions. The results
obtained can be explained taking into account that the
radius of the small cation is surrounded and shielded by a
large number of water molecules. Therefore, the cationic
charge density becomes low and its bonding ability to the
carboxylate group is weak. However, the cation with a large
radius tends to enter the network and easily binds to the
hydrogel carboxylate groups, resulting in decrease of its
swelling capacity. The swelling behavior of H-C-g-PAAm
Fig. 15 Bean plants cultivated in a gel free soil and irrigated with
brackish water (control), b gel free soil with saline water and c H-C-
g-PAAm gel treated soil with saline water
Radiation synthesis of -carrageenan/acrylamide graft copolymers
is also significantly lowered by enhancing ionic strength of
salt solutions. The decrease in swelling ratio of hydrogels
with increasing salt concentration in the external solution is
due to a decrease in the expansion of the hydrogel network
in salt solutions. This is not only due to the decrease in the
osmotic pressure difference between the gel and the
external solution but also due to the screening of the ionic
charges bound to the hydrogel network [27].
Swelling variation with pH
Since the H-C-g-PAAm hydrogels comprise of anionic
sulfate and carboxylate groups, they may exhibit sharp
swelling changes at a wide range of pH values. Therefore,
the equilibrium swelling of H-C-g-PAAm hydrogel was
measured at various buffer solutions with pH ranging from
1 to 13 (Fig. 12). Under acidic pH values, most of the
carboxylate anions are protonated, so the main anionanion
repulsive forces are eliminated and consequently swelling
values are decreased. At higher pH values (58), some of
the carboxylate groups are ionized and the electrostatic
repulsion betweenCOO groups causes an enhancement of
the swelling capacity. Again, a charge screening effect of
the counter ions (cations) limit the swelling at higher basic
pH values (pH>8) [27].
Swelling rate
Figure (13) shows swelling rate of the hydrogels, C-g-
PAAm and H-C-g-PAAm, as a function of swelling time
in distilled water at room temperature. According to
Fig. 13, the swelling rate sharply increases with increasing
time and then begins to level off. There are a similar in
saturation time for the two types of hydrogels, nearly;
180 min.
Application of the prepared H-C-g-PAAm hydrogels
H-C-g-PAAm hydrogels of different compositions were
immersed in saline solution (0.9% NaCl). The salinity of
residual solutions was measured. The relation between the
residual salinity and H-C-g-PAAm hydrogels composi-
tions was determined and is shown in Fig. (14). It was
found that the salinity of 0.9% NaCl solution increased with
increasing C content in C-g-PAAm gel to maximum
value (23 mS/m) at 20/80 C/AAm. This means that the
gels have ability to absorb fresh water from saline solution
i.e the gel possess the ability to desalinate brackish water.
Thus the sodic soil can be reclaimed by using such
hydrogels [14].
The possible use of grafted carrageenan copolymers
super-absorbed hydrogels to adsorb fresh water from saline
water was investigated. Field evaluation of the H-C-g-
71
PAAm hydrogels for its possible uses in agriculture as a soil
conditioner adsorb fresh water from saline water was
investigated in a range of garden plants using bean as a
model plant. As shown in Fig. (15), it is clear that the growth
of bean plants cultivated in the soil treated with H-C-g-
PAAm hydrogels and irrigated with saline water (Fig. 15c)
is greater than those cultivated in gel-free soil and irrigated
with saline water (Fig. 15b). The results suggested that the
hydrogel particles around the bean root can absorb large
quantities of fresh water; thus, soil water retention was
improved, and the available pure water for the plant
increases, resulting in growth promotion of the bean plant.
Conclusion
A superabsorbent hydrogel, H-C-g-PAAm, was prepared
via graft copoly-merization of AAm onto C backbones
followed by alkaline hydrolysis of the C-g-PAAm
copolymer. The swelling capacity of the hydrogels was
recognized to be affected by the grafting and alkaline
hydrolysis variables. The swelling ratio continuously
decreases with increasing irradiation dose and acrylamide
concentration in the feed mixture. The maximum water
absorbency (704 g/g) was achieved under optimum hydro-
lysis conditions (NaOH concentration of 3N, hydrolysis
time 60 min, and hydrolysis temperature 80C). Due to the
polyelectrolyte nature of the prepared hydrogels, they were
sensitive to the pH and ionic strength of the medium. It
exhibited high swelling capacity at basic pH values as well
as a reversible pH-responsiveness property. Swelling
measurements of the synthesized hydrogels in different salt
solutions showed appreciable swelling capacity, especially
in LiCl, NaCl, and KCl solutions. The results suggest that
the H-C-g-PAAm hydrogel can absorb large quantities of
fresh water from saline one. This suggested the possible use
of H-C-g-PAAm hydrogels in agriculture as a soil
conditioner adsorb fresh water from saline water.
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