Egyptian Journal of Petroleum xxx (2018) xxx–xxx

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Egyptian Journal of Petroleum

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Full Length Article

Green chemistry approach for preparation of hydrogels for agriculture

applications through modification of natural polymers and investigating
their swelling properties
Manar Elsayed Abdel-Raouf ⇑, Shimaa Mohmaed El-Saeed, Elsayed Gamal Zaki, Ahmed Mohamed Al-Sabagh
Egyptian Petroleum Research Institute, 1 Ahmed El-zomor Street, Nasr City, Cairo, Egypt

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

Article history: Two sets of hydrogel materials based on guar gum were prepared by grafting guar gum onto acrylic acid/
Received 2 July 2018 acrylamide and acrylic acid/N-isopropylacrylamide copolymers by using persulphate radical as an initia-
Revised 28 August 2018 tor and N,N0 methylenebisacrylamide as a cross linker. The prepared hydrogels were denoted as AA-AcM-
Accepted 24 September 2018
GG and AA-NIPAM-GG respectively. They were characterized by FTIR Spectroscopy and SEM. The effect of
Available online xxxx
some composition variables on the swelling performance of PA-GG hydrogel was thoroughly studied.
Furthermore, swelling behavior was monitored as a function of temperature and electrolyte concentra-
Keywords:
tion. A lab experiment was carried out in order to investigate the effect of the optimum hydrogels on
Guar gum
Acrylate
the growth of guava plant.
N-isopropyl acryl amide Ó 2018 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute. This is
Green hydrogels an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Temperature sensitive
Salt sensitive

1. Introduction Natural polymers can be chemically modified into hydrogels.

The recent concept of green chemistry is spread worldwide due
to a number of environmental and economic considerations. The
replacement of petroleum-based materials with materials derived
from natural sources has become an essential demand. This
requirement is increased tremendously when it comes to products
related to human-health, i.e. medical, pharmaceutical-and food
products. It is well established that the pollution of soil directly
and indirectly affects human well-being and other living organism
and also may destroy the food chain [1–3]. Thus, the materials
based on or derived from natural polymers have attracted great
attention [4–10].
Herbal polymers are biodegradable and show no undesirable
effects on the environment or human being. They are also biocom-
patible, non-toxic and economic [11,12].These materials are
derivatives of either proteins or carbohydrates and found unlim-
ited applications in food industry [13,14], pharmaceuticals [15–
19], tissue engineering [20,21], health care products [22] and
others.
Hydrogels are materials that display three-dimensional network
of hydrophilic polymers which are able to absorb and keep a large
amount of water within its network structure [23]. The network
structure can be achieved by the chemical crosslinking [24], phys-
ical chain entanglement [25], hydrogen bonds [26], and ionic
bonds [27].
The most important natural polymers are cellulose, starch, and
Guar Gum. The present work deals with chemical modification of
Guar Gum into hydrogel materials with different chemical struc-
tures to be used in agriculture applications.
The main objective of the present study is to develop hydrogels
based on crosslinking of natural product (Guar Gum) with different
acrylate monomers (Acrylamide, acrylic acid and N-isopropyl acry-
lamide). The second objective is to investigate their swelling char-
acteristics under different conditions. Furthermore, optimum
samples were used to implant guava plant under drought
conditions.
2. Materials and methods

2.1. Materials
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author. The acrylate monomers (acrylamide, acrylic acid and N-
E-mail address: drmanar770@yahoo.com (M.E. Abdel-Raouf). isopropyl acrylamide) were obtained as analytical reagents from

https://doi.org/10.1016/j.ejpe.2018.09.002
1110-0621/Ó 2018 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
2 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx

Fluka, Germany. Guar Gum (GG, food grade, Mn 220,000) was pur- remove the homopolymers formed in the grafting reaction and
chased from Indian chemical company. Potassium persulfate (KPS), vacuum dried at 40 °C to a constant weight. The percentage of
analytical grade, Aldrich) and N,N0 methylene bisacrylamide (MBA, grafting (%G), was calculated [29–31] by using Eq. (2.1) where
chemically pure, Aldrich) were used as purchased. All other W0 and W1 denote the weight of GG and graft copolymer
reagents were analytical grade and all solutions were prepared respectively.
with distilled water.
W1  W0
% Grafting ð% GÞ ¼  100 ð2:1Þ
W0
2.2. Preparation of PA-GG hydrogels

Two series of PA-GG hydrogels were synthesized by free radical
bulk copolymerization of different acrylate monomers (AM)
(namely, Acrylamide (AcM), acrylic acid (AA), and N-isopropyl
acrylamide (NIPAM)) with varying weight ratios of GG with respect
to AM. The synthesis procedure was modified from Chandrika et al.
[28]. Two quantities of MBA were used for each series in order to
optimize the best hydrogel with respect to its swelling tendency.
The synthesis conditions and designation of hydrogels are also pro-
vided in Table 1.
The initial step of the reaction involves free radical generation
by thermal degradation of potassium per sulfate solution (0.05 g
in 50 mL distilled water) at 60 °C. Then, a neutral AA (pH 7.2–
7.4) solution was prepared by dissolving the predetermined weight
of acrylic acid in 10 mL concentrated NaOH solution (8.0 mol/L).
Afterwards, the equivalent weight of other acrylate monomer
was added into this solution. Then the pre-determined amount of
GG was dispersed in 50 mL neutral AA solution and stirred for
2 h in 250 mL flat bottom flask (Solution A). At this step, KPS solu-
tion was added into solution A and the mixture was stirred for
30 min. holding the reaction temperature at 60 °C (Solution B).
The desired weight of MBA was dissolved in 2–3 mL of distilled
water then added to solution B with constant stirring till a
homogenous dispersion was obtained. Subsequently the content
of the flask was poured into test tubes (the internal surface of
the test tubes is covered with thin layer of silicon oil in order to
facilitate the recovery of the hydrogel rods) and kept in water bath
maintained at 65 °C for 2 h for completing polymerization reaction.
Then, the prepared hydrogel was taken out from the test tube and
cut into small slices of about 0.5 cm-thick. These slices were
weighed and then immersed in distilled water for 24 h in order
to remove any unreacted chemicals. Then they were kept at room
temperature for 12 h and dried in vacuum oven at 50 °C till con-
stant weight.
2.3. Calculation of degree of grafting of guar gum
After the polymerization reaction was completed, the product
was cooled by running tap water and poured into excess of acetone
to induce precipitation. The graft (PA-GG) polymers were washed
several times with methanol:water (80:20 v/v) mixture [29] to
2.4. Characterization
The FTIR spectra of GG, AA-AcM1.5-GG5, and AA-NIPAM1.5-
GG5 were recorded using KBr discs on Perkin-Elmer Spectropho-
tometer in order to verify the formation of PA-GG hydrogels.
In order to investigate and compare the effect of different struc-
tural variables on the morphology of the prepared hydrogels, the
ESEM analysis was carried out for neat GG, AA-NIPAM1.5-GG5,
AA-NIPAM1.5-GG15, AA-NIPAM2.5-GG5 before and after swelling.
ESEMs of these polymers were recorded using Hitachi S3700N
Scanning Electron Microscope.
The crystallinity of the hydrogel was monitored via X-ray
diffraction. (XRD) is an efficient non destructive technique for char-
acterizing crystalline materials. X-ray diffraction (XRD) patterns
were recorded on Philips Xpert pyrosystem Cu Ka radiation (k =
1.54 Å and theta = 0–80°) at ambient temperature.
2.5. Extraction of soluble fraction materials (SF) [32]
The soluble fractions of these polymeric materials were deter-
mined via Soxhlet extraction with chloroform for 24 h. After
extraction the samples were dried to a constant weight in vacuum
oven at 308 K.
The soluble fraction (SF) was expressed as the fractional loss in
weight of xerogel. SF values were calculated according to the fol-
lowing equation
SF% ¼ ððW0  WÞ  100=W0 Þ ð2:2Þ
where W0 and W are the weight of discs before and after extraction
respectively.
2.6. Measurements of water absorption and swelling kinetics [33,34]
Water uptake of the prepared hydrogels was measured by tea
bag method. About 0.05 gm of the sample was placed in a tea
bag then immersed in an adequate amount of distilled water at
room temperature (25 °C) for 30 min. Then the tea bag including
the sample is withdrawn from water then kept for about one min-
ute to remove excess water. The weight of the swollen samples
was recorded versus time. The water absorption of the hydrogels

Table 1
Recipe for the preparation of PA-GG hydrogels.

Code Designation Feed composition (g) % Grafting (% G)

AA AcM/NIPAM GG MBA
AA-AcM-GG AA-AcM1.5-GG5 5 5 0.5 0.15 20.30
AA-AcM1.5-GG10 5 5 1 0.15 10.15
AA-AcM1.5-GG15 5 5 1.5 0.15 6.767
AA-AcM2.5-GG5 5 5 0.5 0.25 19.50
AA-AcM2.5-GG10 5 5 1 0.25 10.25
AA-AcM2.5-GG15 5 5 1.5 0.25 6.833
AA-NIPAM- GG AA-NIPAM1.5-GG5 5 5 0.5 0.15 20.30
AA-NIPAM1.5-GG10 5 5 1 0.15 10.15
AA-NIPAM1.5-GG15 5 5 1.5 0.15 6.767
AA-NIPAM2.5-GG5 5 5 0.5 0.25 19.50
AA-NIPAM2.5-GG10 5 5 1 0.25 10.25
AA-NIPAM2.5-GG15 5 5 1.5 0.25 6.833

Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx
(Qmax, g g1) was evaluated from the mass change before and after
swelling according to the following equation:
weight of sample after absorption
Q max ¼
weight of sample before absorption
Moreover, the rate of absorption was also calculated for the pre-
pared samples from the slope of the curve plotted for absorbed
water versus time.
2.7. Measurement of the water absorption at different temperatures
Swelling efficiency of the prepared hydrogels was monitored at
a predetermined temperature ranging from 15 to 60 °C by tea bag
method then the bags were removed and weighed till constant
weights. After weight measurement at one temperature, the
hydrogels were re-equilibrated at another predetermined temper-
ature for subsequent measurement. The change of Qmax with tem-
peratures was studied.
2.8. Swelling at various salt concentrations
Absorbency of the prepared hydrogels was determined at differ-
ent salt concentrations, 0–1% NaCl solution at 25 °C.
2.9. Effect of the prepared hydrogels on the growth of guava plant
A lab experiment was carried out in order to investigate the
effect of the optimum hydrogels on the growth of guava plant.
The soil was well irrigated then it has been subjected to drought
conditions for 15 days. Then the optimum hydrogel(s) was added
in certain weight and the samples with hydrogels were compared
to the test sample.
2.10. Re-swelling capacities
For the deswelling kinetics measurements, the hydrogels were
swollen in water at 25 °C until equilibrium then they were trans-
ferred into hot distilled water at 50 °C. The weight changes of gels
were measured gravimetrically after plotting the excess surface
water at regular time intervals. For the measurement of the
Scheme 1. Detailed reaction scheme radical formation, propagation, and crosslinking reactions.
Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
3
reswelling kinetics of the gel, the equilibrium collapsed hydrogel
samples at 50 °C were transferred into water at 25 °C. The weight
changes of gels were also determined gravimetrically as described
ð2:3Þ above. The water uptake or the water retention mret was calculated
in terms of the relative gel mass.
mret = mt/msw, Where, mt is the mass of gel sample a time t and
msw is the swollen mass at 25 °C.
3. Results and discussion
3.1. Graft copolymerization
Graft copolymerization was carried out by generation of free
radical in homogeneous solution. Graft copolymerization mecha-
nism was studied in several reports [35,36]. The probable reaction
mechanism of present study is given in Scheme1. Graft copolymer-
ization of acrylate onto GG was achieved by using KPS as a redox
initiator to produce radicals on the polymer backbone [37].
The persulfate initiator was thermally decomposed into sulfate
anion radicals, which abstracted hydrogen atom/s from the hydro-
xyl groups of the GG main chain (mannose chain) to form macro-
molecular radicals. The vinyl groups of AM were then linked to
the active radicals forming covalent bonds and simultaneously cre-
ate the new radicals that can cause the chain propagation. The poly
functionality of crosslinker N,N0 MBA(CH2@CHCONHCH2-
NHCOCH@CH2) resulted in formation of a macro-radical with four
reactive sites which can be utilized for crosslinking both the PAM
and GG through its AOH groups (as shown in Scheme 1). These will
finally result into the formation of three dimensional network of
(PAM-GG) hydrogel.
The values of degree of grafting of the prepared hydrogel
(Table 1) reveal the following:
1. The degree of grafting decreases by decreasing the weight of
guar gum in the polymer chin. This may be due to the decrease
in the amount of the macro-radical required for initiation the
reaction.
2. The increase in the crosslinker concentration decreases the
degree of grafting due to the increase in the crosslinking
density.
4 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx
3. The degree of grafting is the same for each two conuterprties
due to the same weight composition.
Our findings agree with Prashanth and Tharanathan study on
graft copolymerization of chitosan with acrylate monomers [37].
3.2. Characterization of the prepared hydrogels
3.2.1. IR characterization
The copolymerization reaction was established by comparing
the FTIR spectra of GG, AA-AcM1.5-GG5, and AA-NIPAM1.5-GG5
as shown in Fig. 1(a), (b) and (c) respectively. The evidence of
crosslinking of polyacrylamide on GG was confirmed by analyzing
the characteristic peaks of the functional groups present in the
respective hydrogel materials, the interpretation of the most sig-
nificant peaks is summarized in Table 2.
The appearance of the carbonyl group of the acrylic acid and the
amide indicate the grafting reaction of the acrylate monomers onto
the guar gum main chain. Furthermore, the appearance of the NAH
bending vibration is another proof for grafting reaction.
3.2.2. Environmental Scanning Electron Microscope (ESEM)
In order to investigate and compare the effect of the structural
variation (i.e. changing the acrylate monomer, changing the AM:
GG ratio and changing the % of crosslinker) on the morphology of
the prepared hydrogels, the ESEM analysis of some selected sam-
ples was carried out. These samples were elected carefully to fulfill
all the structural changes. The ESEM images of neat GG, AA- AA-
NIPAM2.5-GG5 before and after swelling were provided in Fig. 2
(a–c) respectively.
ESEM observations showed the surface modification of guar
gum after crosslinking reaction. SEM images also revealed that
the pore dimension or mesh size of the investigated hydrogels
changes in accordance with the change of GG content, suggesting
an increase of network densities. There are lots of hydroxyl groups
in GG which are able to form intermolecular hydrogen bonding
with AM or intramolecular hydrogen bonding between the side
chains of GG and its backbones in GG/PNIPAAm IPN hydrogels.
According to Flory’s theory [38,39], a high crosslinker concentra-
tion will induce the generation of more crosslink points and the
increase of crosslinking density. Hence, the denser network struc-
tures might be explained on the bases of intra molecular hydrogen
bonding formation resulting from the enhanced entanglements of
hydrogen bonding generated by the increase of GG content. Upon
Fig. 1. The IR spectrum of GG (a), AA-AcM1.5-GG5 (b), and AA-NIPAM1.5-GG5 (c).
Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
Table 2
The most important peaks and their interpretation.
The Significant peaks and their interpretation
compound
GG 3300–3400 cm1 broad OAH stretch , 2930.5 cm1 (CAH
stretching), 1450–1470 s CAH bend, 1430 cm1 (CAO
stretching of ACH2OH in primary alcohols) and 1150 cm1
(CAOAC stretching in ether)
AA-AcM1.5- The peaks at around 1650–1690 cm1 which is associated to
GG5 C@O stretching with amide group and NH stretching of
amide. 1450–1460 cm1 are due to NH and C@O in plane
bending of amide, 1510–1560 cm-1NAH bend
AA- OAH stretching band of hydroxyl group of GG and NAH
NIPAM1.5- stretching vibration of amide group of AcM and NIPAM
GG15 overlap with each other which can be observed at around
3230–3500 cm1
comparison between SEM images of AA-AcM 2.5-GG5 and AA-
NIPAM2.5-GG5 before and after swelling, (Fig. 2b–d), it can be
observed that the pores are expanded due to water absorption.
Furthermore, regular distribution of the pores and the variation
in their size can be also demonstrated. The ESEM images also prove
that both acrylamide and N-isopropyl acrylamide are very effective
in grafting on guar gum backbone and network formation is
achieved effectively.
3.2.3. XRD analysis
X-ray diffraction patterns of neat GG and AA-NIPAM2.5-GG5 are
given in Fig. 3. It is obvious that Crude guar gum was largely amor-
phous and two peaks were observed at the scattering angle (2-
theta) at 20.5° and 72.4° [40,41]. The grafted composite showed
two peaks at scattering angle (2theta) at 30° and 50.9°. This shows
the development of crystallinity in superabsorbent composite.
3.3. Gel fraction and swelling studies
The soluble non-crosslinked portions can be used as an indica-
tion for the extent of crosslinking. They can be extracted with suit-
able solvents. The data for SF% are given in Table 3. It is obvious
that they depend on:
 The type and concentration of the monomers:
The soluble fraction percentage is higher in the group contains
NIPAM than those of the group contains AM, which may be due to
 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx 5

Fig. 2. The ESEM images of neat GG and some selected hydrogels.

the difference in reactivity between the two monomers. Moreover,
SF% decreases by increasing the concentration of guar gum due to
the denser networks formed by Guar gum [42].
 The type and concentration of crosslinking agent.
It was found that the percentage of SF is reduced when crosslin-
ker content increases from 1.5% to 2.5% (w/w)
3.4. Swelling behavior of the prepared hydrogels
Hydrogels used for soil modification must possess high water
capturing capability and high water retention [43,44]. These proper-
ties increased if the hydrogel has the capability of drawing water into
the material matrix, which implies a porous structure [45]. To exam-
ine the effect of structural variation on water absorption efficiency of
the prepared hydrogels, the amount of water absorbed at equilib-
rium given in g/g of hydrogel Qeq was plotted versus time in neutral
swelling medium (i.e.pH 7) at 25 °C. These data are given in Fig. 4a
and b for AA-NIPAM-GG and AA-AcM- GG respectively. The swelling
characteristics of the prepared hydrogels are given in Table 3.
It can be seen that the amount of water absorbed at equilibrium
Qequ. varies according to the following factors:
 The weight percentage of Guar Gum:
GG is stabilized by periodic intramolecular hydrogen bonds
between the galactosyl side chains and the mannan main chain

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6 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx

Fig. 3. XRD patterns of Guar Gum (Above) and AA-NIPAM2.5-GG5 (Below).

Table 3
%SF, Swelling, and network parameters of the guar gum based hydrogels at 25 °C.

Designation Swelling parameters and soluble fraction data Network parameters

Wt.% of crosslinker SF% Qequ (g/g)* T (min) dQequ/dt** ve Mc (g/mole) v Up d(qp)
mol/dm3 g/l
AA-AcM1.5-GG5 1.5 32.4 170 78 1.355 0.235 466.38 1.133 0.005882 1.15
AA-AcM1.5-GG10 1.5 24.6 160 100 1.330 0.254 342.71 1.330 0.006250 1.18
AA-AcM1.5-GG15 1.5 20.3 140 65 1.324 0.257 301.48 1.355 0.007143 1.21
AA-AcM2.5-GG5 2.5 24.2 166 112 1.203 0.256 392.33 1.116 0.006024 1.17
AA-AcM2.5-GG10 2.5 16.9 145 113 1.133 0.433 308.06 1.203 0.006897 1.22
AA-AcM2.5-GG15 2.5 8.5 135 110 1.116 0.478 217.18 1.324 0.007407 1.28
AA-NIPAM1.5-GG5 1.5 35.7 220 78 1.544 0.204 498.67 1.267 0.004545 1.18
AA-NIPAM1.5-GG10 1.5 28.8 200 81 1.538 0.215 359.56 1.377 0.005000 1.23
AA-NIPAM1.5-GG15 1.5 20.4 180 85 1.466 0.277 332.26 1.466 0.005556 1.27
AA-NIPAM2.5-GG5 2.5 24.9 200 80 1.518 0.289 268.88 1.318 0.005000 1.24
AA-NIPAM2.5-GG10 2.5 16.1 192 93 1.455 0.408 258.69 1.455 0.005208 1.28
AA-NIPAM2.5-GG15 2.5 12.4 158 117 1.318 0.811 158.79 1.518 0.006329 1.31
*
Maximum water absorption Qequ. at 25 °C.
**
Rate of absorption dQequ/dt.

[46]. When it is combined with PAA, intermolecular hydrogen
bonds between GG and PAA are formed. It can be observed that
(Qequ.) decreases with increasing the GG from 5 wt% to 15 wt%. This
may be attributed to decreasing the percentage of ionic acrylate
groups within the polymer network with the increase in the ratio
of Guar Gum to acrylate in the entire network structure. This find-
ing is consistent with Ria et al’s results [47] and Chavda [48].
 The weight percentage of crosslinker:
It can be also observed that Qmax sharply decreases with
increasing the crosslinker concentration from 1.5 to 2.5 wt%. These
results are consistent with the data of network parameters dis-
cussed in the previous section. Pourjavadi et al. stated that there
is an optimum crosslinker concentration required for harmonic

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ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx 7

Fig. 4. Maximum water absorption for the prepared hydrogels at 25 °C.

network structure. The over-crosslinking hinders the mobility of
polymeric chains and thus lowers the swelling of hydrogels [49].
We found that the hydrogels with lower crosslinker concentration
(1.5%) showed better swelling efficiency than the corresponding
ones with higher crosslinker concentration.
 The weight percentage of acrylate monomer:
It was reported [50,51] that the incorporation of amine group,
i.e. acrylamide or N-isopropyl acrylamide altered the arrangement
and distribution of intra and intermolecular hydrogen bonding. In
this work, it was found that the hydrogels with N-isopropyl acry-
lamide had higher Qequ. than those contain acrylamide. This may
be attributed to the positive inductive effect of isopropyl group
which induces stronger hydrogen bonding for the amine group.
3.5. Network parameters
The data given in Table 3 are for: the effective crosslink density
(te), molecular weight of the chains between two successive cross-
links (Mc), polymer-solvent interaction parameter (v), volume
fraction of the polymeric material in the dry gels (Up) and density
of the dry gels. The temperature coefficient of polymer volume
fraction (d Up/dT) was determined and utilized to calculate v. It
is established that the lower the values of v, the higher the
polymer-solvent interaction [48]. All these values can be calculated
from the following equations
The theoretical crosslink density mt has been calculated from:
vt ¼ Cf=2 ð3:1Þ
where C (mol L1) is the concentration of crosslinking agent of func-
tionality f. For MBA, f = 4. The value of C was determined from the
weight concentration of MBA and the density q of the xerogel.
The latter was determined by direct weighing and micrometrically
measured dimensions of the dried discs.
The molar mass between crosslinks (Mc) can be calculated from
the Flory-Rehner equation [38,39], the temperature coefficient of
volume fraction (dUp/dT) may be obtained as:

 
 

dUp =dT ¼vUp T  1 2Up v  Up 1  Up   ln 1  Up þ Up
i o 1
þ vU2p N ð3:2Þ

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8 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx


Where; N ¼ ð1=3 Up2=3  2=3Þ Up1=3  2=3Up
1
ð3:3Þ tion. Upon comparing v parameter of the AA-NIPAM-GG with those
of AA-AcM-GG at the same crosslinker concentration, it was found
Solving Eq. (3.3) we get the value of v as follow: that v values are less for the former hydrogels than those for acry-
h
1
 i lamide counterparts due to increased polymer-solvent interaction.
v ¼ Up 1  Up þ N ln 1  Up þ NUp Furthermore; the densities of the prepared hydrogels (qp) are all
h
l i1 more than unity. This indicates that the prepared dry gels can be
 2Up  Up 2N  Up 2Tl dUp =dT ð3:4Þ mixed with the soil content.
Values of Up listed in Table 3 measured at 25 °C increases with
The molar mass between crosslinks can then be estimated as: increasing both the concentration of crosslinking agent and the
h
 i1 content of guar gum due to increased network intensity. The cross-
Mc ¼ qp ms Up1=3 ln 1  Up þ Up þ vU2p ð3:5Þ link density te and average molecular weight between crosslinks
Mc are the key variables, which control the swelling capacity. It
where ms is the molar volume of water at different temperatures, qp can be shown that, te increases with increasing guar gum content.
is the density of polymer. ms can be calculated as following This runs in harmony with the values of Qequ which decrease by
ms ¼ 103 ½MWt of water=density ð3:6Þ increasing the guar gum content which affects the ability of the
hydrogel to retain water due to increased possibility of physical
It is observed that v have values ranging from 1.133to 1.355 for AA- crosslinks.
AcM-GG at 1.5% crosslinker, and it also increases by increasing the The data show that Mc values decrease as crosslinker weight
weight percentage of guar gum reflecting polymer – water interac- content increase and with increasing guar gum content in the poly-

Fig. 5. Temperature dependence of maximum water absorption of (a) AA-NIPAM-GG hydrogels, (b) AA-AcM-GG hydrogels, (The black line represents maximum water
absorption at 15 °C (The blue vertical line drawn at 25 °C representing data that appears in Table 3).

Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx 9

Fig. 6. Effect of water salinity on maximum water absorption of (a) AA-NIPAM-GG hydrogels and (b) AA-AcM-GG hydrogels at 15OC.

3.6. Factors affecting equilibrium swelling

3.6.1. Effect of temperature change on swelling and water absorption

properties [54,55]
The maximum water absorption of hydrogels Qmax as a func-
tion of changing temperature in the range of 15–50 °C/60 °C is
given in Fig. 5a and b for AA-NIPAM-GG and AA-AcM-GG,
respectively.
Careful investigation to Fig. 5a and b, the following behaviours
are observed:

(i) The thermo-responsive behavior of the AA-NIPAM-GG

Fig. 7. Effect of hydrogels on guava plant after 20 days of implantation Control, B-0.
3% of AA-NIPAM2.5-GG5, C-0.3% of AA-AcM2.5-GG5 and D- 1:1 AA-NIPAM2.5-GG5:
AA-AcM2.5-GG5).
mer network. This finding may be due to that the increase in the
amount the crosslinking agent led to formation of a denser net-
work of the crosslinked reactive copolymer and reduce Mc. In other
words, the smaller Mc value indicates the higher crosslinking den-
sity network. On the other hand, the crosslinking density increase,
the hydrogel absorbing capacity is reduced [52,53].
hydrogels is very pronounced where they lost all the
absorbed water when the temperature approached the
lower critical solution of NIPAM.
(ii) The swelling capacities for hydrogels with the same GG
amount, AA-NIPAM1.5GG5 and AA-NIPAM2.5 GG5,
decreased as the % of crosslinker increased due to the
increase of network density (i.e., the crosslink density).
(iii) Water absorption capacities were reduced by the increase in
Guar Gum content in the hydrogel structure due to increas-
ing in the crosslink density.
(iv) AA-AcM-GG hydrogels show different thermo-responsive
behavior. Basically, they achieve slow extended water
release from 15 to 60 °C. Thus, they provide higher water
retention than AA-NIPAM-GG hydrogels.

Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
10 M.E. Abdel-Raouf et al. / Egyptian Journal of Petroleum xxx (2018) xxx–xxx
Fig. 8. Swelling/deswelling cycles of the prepared hydrogels in fresh water at 25 °C and pH 7.
(v) Blended formulations of both types of hydrogels can induce
dual function to the soil, i.e. slow water release, and modi-
fied water retention.
3.6.2. Effect of salt concentration on swelling properties
The effect of salt concentration on water absorption was carried
out at 15 °C in neutral medium, Fig. 6a, and b for AA-NIPAM-GG
hydrogels and AA-AcM-GG hydrogels respectively. It is obvious
that the prepared hydrogel show considerable salt response and
increases water salinity affects maximum absorption for all the
investigated hydrogels. This well-known undesired swelling-loss
is often attributed to a ‘‘charge screening effect” of the additional
cations causing a non-perfect anion-anion electrostatic repulsion
[56].
Therefore, the osmotic pressure resulting from the portable ion
concentration difference between the gel and aqueous phases
decreased and consequently the water absorbency decreased.
However, The NIPAM based hydrogels show regular water release
with sharp peak at 0.3–0.4% salt concentration, whereas the AcM
hydrogels follow irregular behavior. This may be related to the dif-
ference in hydrogel structures with respect to the N-isopropyl
group and the Acrylamide group.
3.7. Effect of the prepared hydrogels on the growth of guava plant [57]
A lab experiment was carried out in order to investigate the
effect of the optimum hydrogels on the growth of guava plant,
Fig. 7. The soil was well irrigated then it has been subjected to
drought conditions for 15 days. It is clear that the addition of
hydrogel improved the total vegetative parts of the plants in
drought conditions which reflect the modification of water reten-
tion capacity of the soil. Also, it can be seen that the growth of
plant implanted in the soil treated with AA-NIPAM2.5-GG5 is
enhanced over the one in soil treated with AA-AcM2.5-GG5. The
plant with mixed hydrogel (D) showed better growth than that
with AA-AcM2.5-GG5.
3.8. Reswelling capacities
Fig. 8 illustrated three swelling/deswelling cycles for the pre-
pared hydrogels at 25 °C. It is noticeable that Qmax decreases from
cycle to another. However, at the third cycle, the hydrogels could
still absorb reasonable amount of water. The reswelling ability
depends on the hydrogel structure [58]. The hydrogel with higher
crosslink density possess lower water absorption by time due to
Please cite this article in press as: M.E. Abdel-Raouf et al., Green chemistry approach for preparation of hydrogels for agriculture applications through mod-
ification of natural polymers and investigating their swelling properties, Egypt. J. Petrol. (2018), https://doi.org/10.1016/j.ejpe.2018.09.002
reduced elasticity. Moreover, the NIPAM group showed better
usability than the AcM which may be due to the isopropyl group
providing some elasticity to the hydrogel structure which modifies
water absorption capacity.
4. Conclusions
Two sets of Guar Gum based hydrogels where prepared by
crosslinking guar gum with mixed acrylate monomers. The first
set involves acrylic acid and acrylamide and the second set
includes N-isopropyl acrylamide replacing acrylamide. The first
set showed better water retention whereas the second set proved
better thermo-responsive properties. The maximum swelling
capacity of the prepared hydrogels decreased by increasing the salt
concentration, this may be due to cation-anion interaction. More-
over, swelling-deswelling investigation confirmed the usability of
the prepared hydrogels up-to three cycles with reasonable water
absorption.
Acknowledgment
The authors acknowledge Academy of scientific research and
technology (ASRT), Egypt, for funding this work (Jessor 1013-
2016).
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