Carbohydrate Polymers 191 (2018) 152–160

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

Super water absorbing polymeric gel from chitosan, citric acid and urea: T
Synthesis and mechanism of water absorption
Abathodharanan Narayanan, Ravishankar Kartik, Elanchezhian Sangeetha,
⁎
Raghavachari Dhamodharan ,1
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India

A R T I C LE I N FO A B S T R A C T

Keywords: A new superabsorbent with maximum water absorption capacity of ∼1250 g/g is prepared by hydrothermal
Superabsorbent synthesis from sustainable and biodegradable resources such as chitosan, citric acid and urea (denoted as
Macroporous polymer ‘CHCAUR’). CHCAUR is characterized extensively by various analytical techniques such as PXRD, SSNMR, FTIR,
Water retention in soil and TGA. Pure and saline water absorption study showed that CHCAUR could be a better adsorbent compared to
Chitosan
the super absorbent polymer (SAP) used in commercial diaper material. The mechanism of water absorption is
Hydrothermal synthesis
shown to arise out of a combination of electrostatic attraction of water to the ionic crosslinks and the presence of
macropores as well as undulated surface due to the formation of nanofibrous bundles. When applied to soil
CHCAUR was found to decrease water evaporation rate significantly.

1. Introduction
Super absorbing polymers (SAPs) absorb and retain very large
quantity of liquid up to several hundred times their own weight
(Omidian, Rocca, & Park, 2005) and when the liquid being absorbed is
water they find application in fields such as agriculture, personal hy-
giene, etc. There are two main classes of SAPs: synthetic (petrochemical
based) and natural (biopolymers). The SAPs used in commercial ap-
plications are manufactured from non-renewable petrochemical re-
sources and especially from acrylic acid and acrylamide based mono-
mers (Krul et al., 2000). Every year, several million metric tons of
synthetic SAP materials are produced and used for different applica-
tions. The World’s consumption of SAP is many orders of magnitude
more for personal hygiene and health care than any other application
(“Super Absorbent Polymer (SAP) Market: Global Industry Analysis and
Opportunity Assessment 2015 – 2020,” n.d.). Hydrogels, a special form
of SAPs, exhibit water absorption capacity in the vicinity of 100%, swell
in water and retain a significant fraction of water (> 20%) within their
structure without dissolving (Buchholz & Graham, 1998). The flex-
ibility of hydrogels is comparable to natural tissue due to the flexible
macromolecular component and water content and therefore is gaining
importance as scaffolds in tissue engineering.
The disposal of SAPs after use in landfill causes pollution in the
environment as they do not biodegrade within reasonable period in
nature (Zohuriaan-Mehr et al., 2008) and hence there continues to be
interest in developing SAPs that are part synthetic and part natural. In
this context, the synthesis of SAP material through graft copolymer-
ization of synthetic monomers with biopolymers such as cellulose,
chitosan, starch, alginates and their derivatives as one of the in-
gredients has been reported. These materials by design are not fully
biodegradable, since the grafts such as poly(acrylate) or poly(acryla-
mide) or poly(acrylic acid) are not biodegradable (Liu et al., 2017; Liu,
Miao, Wang, & Yin, 2009; Omidian, Rocca, & Park, 2006; Ye, Tang,
Hong, & Hui, 2016). Among the biopolymers, the preparation of graft
copolymers of chitosan with acrylic acid, acrylates, acrylonitrile and
acrylamides acquired significance in applications demanding high
water uptake capacity (Fernández-Gutiérrez et al., 2016; Huacai, Wan,
& Dengke, 2006; Mahdavinia, Pourjavadi, Hosseinzadeh, & Zohuriaan,
2004; Zhang, Wang, & Wang, 2007). Water absorption capacity in the
range 150–650 g/g has been reported. It was shown that chitosan-
starch citrate crosslinked polymer exhibited high water uptake in water
as well as saline medium (Salam, Pawlak, Venditti, & El-Tahlawy,
2010).
The most important challenge in the area of biodegradable SAPs is
to synthesize or fabricate fully biodegradable polymer based super-
absorbing materials that would rapidly and reversibly absorb water
with good mechanical strength. For this purpose biopolymers such as
starch, cellulose and cellulose derivatives, chitosan, and marine poly-
saccharides would be most ideal. Among the biopolymers, chitosan is
more promising for application in super water absorbency in view of

⁎
Corresponding author.
E-mail address: damo@iitm.ac.in (R. Dhamodharan).
1
This work constitutes a part of patent application No. 2505/CHE/2015.

https://doi.org/10.1016/j.carbpol.2018.03.028
Received 25 October 2017; Received in revised form 13 February 2018; Accepted 12 March 2018
Available online 14 March 2018
0144-8617/ © 2018 Published by Elsevier Ltd.
A. Narayanan et al.
several important properties such as biodegradability (Salam et al.,
2010; Vårum, Myhr, Hjerde, & Smidsrød, 1997), biocompatibility
(Hirano and Noishik., 1985) and bioactivity (Domard, Domard, & Lyon,
2002). Chitosan is reported to be haemostatic (Malette, Quigley,
Gaines, Johnson, & Rainer, 1983), fungi- and bacteria- static (Strand,
Vandvik, Vårum, & Østgaard, 2001). It is also known to support cell
proliferation and tissue regeneration (Boucard et al., 2007;
Montembault et al., 2006). The preparation of a multi-membrane
structured material based on chitosan and sodium alginate without an
external crosslinker was reported (Ladet, David, & Domard, 2008). The
presence of an amino group and a primary as well as secondary hy-
droxyl groups per repeat unit of chitosan makes it a hydrophilic
polymer (Hamed, Özogul, & Regenstein, 2016; Martínez, Blanco,
Davidenko, & Cameron, 2015; Zohuriaan and Kabiri, 2008). An inter-
esting recent example demonstrates that a mixture of polysachcharide
(comprising of carrageenan and calcium alginate) functions as a fast
swelling composite absorbent for saline water with high mechanical
strength. (Ye et al., 2016). The preparation of superabsorbing materials
from polysaccharides and proteins (Ichikawa & Nakajima, 1996) as well
as shellfish waste (Dutkiewicz, 2002; Ichikawa & Nakajima, 1996) have
been reviewed.
The use of chitosan or chitosan based materials as SAP demands that
the physicochemical properties of chitosan be studied to take advantage
of the delicate balance between the hydrophobic (-NHCOCH3) and
hydrophilic (eOH and eNH2) groups (Schatz, Viton, Delair, Pichot, &
Domard, 2003; Sorlier, Denuzire, Viton, Domard, & Denuzie, 2001) and
optimize the physical microstructure (Spagnol et al., 2012; Vunain,
Mishra, & Mamba, 2016; Zhang, Zeng, & Cheng, 2016). Porous films
and three dimensional scaffolds of chitosan were prepared by freeze
drying its solution in aqueous acetic acid. This resulted in pore size and
pore thickness larger than several hundreds of micrometers (Anitha
et al., 2014; Esquerdo, Cadaval, Dotto, & Pinto, 2014; Kim et al., 2011;
Madihally & Matthew, 1999). Such films and scaffolds exhibited rela-
tively less and slow water uptake due to low specific surface area that in
turn results in less exposure of water to hydrophilic groups present in
the backbone.
The method of direct crosslinking of polysaccharides and more
specially cellulose derivatives with divinyl sulphone/epichlorohydrin/
glyoxal/POCl3/citric acid is well known (Demitri et al., 2008; Sannino
et al., 2003). An interesting recent development in this area is the
synthesis of SAP using citric acid as one of the monomers (Kim, Koo,
Kim, Hwang, & Im, 2017). An important recent development as far as
using chitosan as a superabsorbent, is the successful preparation of
nanoporous chitosan films from dioxane, DMSO and aqueous acetic
acid, a ternary solvent system, which is noteworthy in many aspects
(Wang, Lou, Zhao, & Song, 2016).
Recently, we reported on the synthesis ad characterization of a SAP
based on chitosan, EDTA, and urea (CHEDUR). The maximum water
absorption capacity of this material was 500 g/g (Narayanan &
Dhamodharan, 2015). The high water absorption of CHEDUR was
proposed to result from the presence of macro pores in the pre-
dominantly chitosan matrix as well as due to the presence of oligomers
of EDTA and urea that were present in smaller quantity and possibly
functioned as crosslinks between the chitosan molecules. This study left
us with few unanswered questions such as: can natural multifunctional
acids replace EDTA? the precise mechanism of high water uptake, the
mechanical properties of the gels (whether they can be tuned), biode-
gradability of the product, exploring specific applications. In this work,
the synthetic methodology adopted for the preparation of a SAP using
chitosan, urea and citric acid is reported (CHCAUR). The structure of
CHCAUR is elucidated by extensive analytical tools, its water absorp-
tion capacity and water retention in soil are also presented in this
paper.
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Carbohydrate Polymers 191 (2018) 152–160
2. Materials and methods
2.1. Materials
Raw chitosan (Mn = 48700 Da; 80% deacetylated as determined by
FTIR; (Muzzarelli, Tanfani, & Scarpini, 1980)) was purchased from M/s.
Matsyafed, Kochi. Citric acid (GR grade), 25% v/v ammonia solution
(GR grade), urea (GR grade), and methanol (GR grade) were purchased
from M/s. Vijaya Scientific Company, Chennai and used without further
purification. Water absorbing material from “Huggies” [Kimbery-Clark
Lever Ltd.] commercial baby diaper was used.
2.2. Synthetic methodology for the preparation of CHCAUR and control
reactions
The new material was prepared by reacting hydrothermally chit-
osan with citric acid and urea in the weight ratio of 1:2:2 and denoted
as CHCAUR. The reaction was performed in a cylindrical stainless steel
reactor of volume 900 mL that was closed permanently at the bottom.
The required quantity of powdered chitosan, citric acid and urea were
added to the reactor through the top. Then the desired amount of water
(66 mL/g of chitosan) was added and the mixture was stirred well for
10 min at room temperature. During this process the solution turned
very thick forming a highly viscous mass. The pH was found to be be-
tween 5 and 6. It was then sealed securely with a circular SS flange and
a Viton ‘O’ ring that was placed in between the lid at the top and bottom
part of the reactor and tightened. The reactor was then placed in a
programmable hot air oven and heated. For all the preparations, the
same heating program was used: heating from 35 °C to 100 °C at 5 °C
per min followed by isothermal heating at 100 °C for 650 min. After this
duration, the reactor was allowed to cool to room temperature under
ambient conditions. The product obtained was a gel (pH = 7 to 7.5
irrespective of the composition of the gel) and this was rinsed with basic
methanol solution (pH 8). This step was repeated several times to re-
move the unreacted substances and other byproducts that could be
present in the gel, as confirmed by analytical methods such as PXRD,
SSNMR and FTIR. The gel thus obtained was dried in a hot air oven
maintained at 50 °C overnight to remove the residual solvent. The
product was powdered well using agate mortar and packed in airtight
bottle for further studies. The water to chitosan ratio was varied be-
tween 200 mL/g to 50 mL/g to prepare gels of different water absorp-
tion capacity. The batch size varied between 3–10 g of chitosan. The
preparations at the 10 g scale were carried out thirty times and were
found to be reproducible as assessed by PXRD, SSNMR and FTIR.
Three control reactions were performed to understand the forma-
tion of CHCAUR. The first one was the reaction between chitosan and
citric acid and the product obtained was denoted as CHCA. The second
was the reaction between chitosan and urea and the product obtained is
denoted as CHUR. The third control reaction was performed between
citric acid and urea and the product was denoted as CAUR. For all these
control reactions the reaction composition and conditions were similar
to that used in the preparation of CHCAUR and mentioned above.
3. Characterization
Gel permeation chromatography of chitosan was performed using
Waters GPC (two ultra-hydrogel 250 SS columns 30 cm × 7.8 mm;
0.1 N sodium nitrate in 20 mL glacial acetic acid and 1000 mL water as
the mobile phase, 0.8 mL/min flow rate) equipped with a RI detector.
Narrow molecular weight PEG standards were used for calibration.
Powder x-ray diffraction pattern was recorded using Bruker D8
Advance diffractometer equipped with Cu anode (Cu Kα source of the
wavelength of 1.5406 Å) between 5–60° (2&z.Theta;). Differential
scanning calorimetry was performed using TA Instruments Q200 MDSC.
The thermal decomposition of all the materials was studied using TA
Instruments Q500 Hi-Res TGA. Around 5 mg of sample was taken in a Pt
A. Narayanan et al.
Fig. 1. Process flow chart representing the preparation of CHCAUR.
pan and heated from 35 to 950 °C at 10 °C per min heating ramp with
the sample purged by nitrogen flow at the rate of 60 mL per min. FTIR
was carried out using JASCO 4100 FTIR spectrometer (JASCO, Japan).
3–5 mg of the sample was mixed with 100 mg of dry KBr followed by
grinding to a very fine powder. This solid mixture was then pressed into
a transparent pellet using a hydraulic pelletizer. The spectrum for this
pellet was recorded after baseline correction. The wave number region
selected for recording is 4000–400 cm−1. NMR spectroscopic mea-
surements in solution were carried out with Bruker spectrometers
(operating at 400 MHz as well as 500 MHz for proton in suitable sol-
vents). Solid state NMR measurements were carried out using Bruker
Avance III spectrometer (Bruker) operating at 400 MHz for 1H and
100 MHz for 13C. The NMR in the solid state (CPMAS) was taken under
the following conditions: spinning rate 10,000 Hz, repetition
time = 5 s, contact time = 2000 μsec, number of scans = 10000. HR
MASS spectrum for unit mass was recorded using Q-Tof micromass
mass spectrometer. Low vacuum SEM images were taken using Quanta
200 Model SEM with Low Field Detector (acceleration voltage = 30 kV;
chamber pressure 100 Pa).
3.1. Water absorption studies
The water/saline absorption study was carried out as described in
our earlier work (Narayanan & Dhamodharan, 2015). Around 20 mg of
well powdered (particle size less than 53 μm) and dried sample was
exactly weighted (w1) and taken in a filter cone. This was placed on top
of a 100 mL beaker filled with distilled water/saline water such that the
sample was well immersed inside the liquid. After the desired time
intervals, the filter cone was removed from the beaker and allowed to
drain liquid for 5 min. After this, the tip of the filter cone was gently
touched once with dry tissue paper and the weight of swollen gel was
determined (w2). The water/saline water absorbed per gram of material
was calculated from the formula (w2-w1)/w1. This was repeated till the
water/saline water absorption capacity reached saturation.
Water retention in soil was carried out at 35 °C for dry soil samples
loaded with 4 wt% of CHCAUR. Prior to the experiment, the soil sample
was powdered and sieved to get particles of size less than 100 μm. This
was dried at 80 °C overnight to remove volatile matter. 19.2 g of dried
soil, 0.8 g of CHCAUR and 30 g of water were taken in a porous pot and
mixed well. The weight of this pot containing the mixture was taken
(w1). This was kept in a hot air oven maintained precisely at
35 °C ± 0.1 °C. After every half an hour time the weight was taken
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Carbohydrate Polymers 191 (2018) 152–160
(w2). The initial water content of the soil was calculated as [30/
(19.2 + 0.8 + 30)]*100 = 60%. The water content of the soil after
each half an hour was calculated as [60-(w1-w2)*100].
4. Results and discussion
A crosslinked gel (CHCAUR) is formed when chitosan, citric acid
and urea were heated in aqueous medium, inside a closed container, at
100 °C. The crosslinking of the gel could arise due to the protonation of
chitosan by citric acid (being a trifunctional acid) resulting in physical
crosslinks through ionic bonds. In addition, the reaction of chitosan
with urea as well as the product of the reaction between urea and citric
acid could also be additional reasons for the formation of a crosslinked
network of chitosan. It may be noted that the reaction between citric
acid and urea, resulting in the formation of an intermediate product
(Paleckiene, Sviklas, & Šlinkšiene, 2005)] and the reaction between
urea with alcohol in presence of an acid, resulting in the formation of
carbamate bond (NH3-CO-O-R) (Lei, Wang, & Li, 2009)], have been
reported. Due to the above reactions the viscosity of the medium in-
creases and gelation occurs. This phenomenon is noticed visibly when
the reaction was performed in a semi-transparent polypropylene bottle.
During the initial 2–3 h of heating the reaction mixture was a thick
mass, which becomes highly viscous liquid in 4–5 h. On further heating,
gas evolution is seen by way of frothing in the reaction mixture. After
650 min of reaction, thick gel was formed with plenty of entrapped gas
bubbles as shown in Fig. 1.
The formation of highly porous gel could be due to the evolution of
ammonia and carbon dioxide gases as urea is known to react with citric
acid forming urea citrate adduct, which decomposes to ammonia and
carbon dioxide (Shaw & Bordeaux, 1955). The formation of carbon
dioxide during the decomposition of citrate salts under pressure is also
known. This interpretation is supported by the increase in the pH of the
reaction to 7.2 after the completion of reaction and the conspicuous
smell of ammonia noticed upon opening the reaction vessel to atmo-
sphere after the reaction.
To understand the reaction between citric acid and urea the product
CAUR formed in one of the control reactions was investigated by mass
spectrometry. This showed the presence of a mixture of citric acid-urea
adducts of varying molecular weights with m/z values of 400, 592, 783,
975… etc., with 192 m/z (citric acid) being the difference between
successive peaks (Supplementary Material Fig. S1). In the light of the
above observation and the literature on the formation of urea-citric acid
A. Narayanan et al.
adducts as well as the known reaction between urea and a hydroxyl
functional group, the following scheme is proposed for CAUR oligomer
formation.
The reaction of alcohol with urea to form carbamate as well as or-
ganic carbonates (on further reaction with one more alcoholic group)
with ammonia evolution has been reported (Shaikh & Sivaram, 1996).
Accordingly in the scheme proposed above, the tertiary hydroxyl group
of citric acid reacts with the eNH2 group of urea and forms carbamate
bond with liberation of ammonia as shown in the above scheme [Molar
mass 235 and molecular formula C7H9NO8]. The carbamate loses one
molecule of ammonia and carbon dioxide upon reaction with a mole-
cule of citric acid to form the product with molar mass and m/z value of
400 and molecular formula C12H20N2O13 as shown in the scheme. The
addition of one more molecule of urea and citric acid and the elim-
ination of a molecule each of ammonia and carbon dioxide results in the
structure with molar mass and m/z value of 591.1. This chemical re-
action process repeats resulting in the formation of species with molar
masses of 783.2 and 973.2 and so on. The formation of the species
shown in the above scheme is not only supported by mass spectrometry
but also reinforced by NMR spectroscopic data (Supplementary Mate-
rial Figs. S2 to S12). The increase of pH and the formation of ammonia
gas during the reaction provide additional proof for the proposed re-
action pathways. CAUR was found to be highly hygroscopic and the
above structures support this observation.
The structure of the crosslinked polymer formed in the above re-
action (CHCAUR) was analyzed by powder x-ray diffraction method.
The diffraction pattern of CHCAUR as well as CHCA, CHUR (products
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Carbohydrate Polymers 191 (2018) 152–160
obtained in the control reactions CHCA − chitosan and citric acid,
CHUR-chitosan and urea under same conditions of CHCAUR prepara-
tion.) and raw chitosan are shown in Fig. 2. Raw chitosan powder
shows two distinct peaks at 2&z.Theta; values of 9.31 and 20.35
emerging due to the reflections from (020) and (110) planes as shown
in Fig. 2 (i). There is significant decrease in the intensity of the (020)
plane in CHCAUR as well as CHCA as seen in Figs. 2 (ii) & (iv). Such a
decrease is not noticed in CHUR (Fig. 2 (iii)), which suggests the de-
struction of higher order crystallinity in chitosan. The PXRD of CAUR
(highly viscous liquid) reveals its amorphous nature (Supplementary
Material Fig. S13). In fact, differential scanning calorimetric analysis
(Supplementary Material Fig. S14) of CAUR confirmed its amorphous
nature as evident from the glass transition temperature of around
−32 °C (at the heating rate of 10 °C/min).
The solid state NMR spectrum of CHCAUR, CHCA, and CHUR are
shown in Fig. 3. The peak values in ppm are given in Table.1. The peak
assignments was done based on literature reference for chitosan (Huang
et al., 2015; Tabeta, Division, & Ogawa, 1987).
The solid state NMR spectrum of CHCAUR shows all the char-
acteristic peaks of chitosan as indicated in Table 1 and in addition three
A. Narayanan et al. Carbohydrate Polymers 191 (2018) 152–160

Fig. 2. PXRD patterns of (i) raw chitosan, (ii) CHCA, (iii) CHUR, (iv) CHCAUR.

Fig. 3. Solid state NMR spectrum of (i) CHCA, (ii) CHUR and (iii) CHCAUR.

peaks at 45.54 ppm (from secondary carbon atoms of citric acid), citric acid in different chemical environments). This confirms the for-
161.21 ppm (carbonyl group of urea) and multiple peaks between mation of adduct involving chitosan, citric acid and urea and that the
177–182 ppm with peak maximum at 178.54 ppm (from the eCOO− of product is stable in the basic methanol medium used to isolate it.

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Table 1
SSNMR peak assignments for CHCA, citric acid, urea, CHUR and CHCAUR

Peak 2 and 10 of CHCAUR (highlighted) are assigned to the eCH2eCH2e and eCOO− group of citric acid incorporated into chitosan polymer chain
respectively.

The SSNMR of CHCA shows seven peaks at 23.2 ppm (-CH3), The absorption of water by CHCAUR as well as the SAP material
57.3,60.9,74.9,87.3,104.7 ppm, respectively (corresponding to C2,C6, used in Huggies diaper with time was carried out and the results are
C3&C5,C4,C1 carbon atoms of chitosan repeat unit shown above), and presented in Fig. 4. The water absorption versus time plot for 0.1%
174.03 ppm (-NH-COeCH3), which matches well with the values re- sodium chloride solution is shown in Supplementary Material Fig. S17.
ported in the literature for chitosan (Heux, Brugnerotto, Desbrières, The presence of ions in water affects the water absorption capacity of
Versali, & Rinaudo, 2000). It is to be noted that even though CHCA is SAPs. This can be quantified by an equation f = 1 − (swelling saline/
most likely to be protonated by citric acid during the course of the swelling in distilled water) (Guilherme et al., 2015). Accordingly f value
reaction, no characteristic peaks of pure citric acid (that is 44.3 ppm for was calculated for CHCAUR and found to be 0.639 when 0.1% sodium
secondary carbon atom) and 76.9 ppm (tertiary carbon atom) was ob- chloride solution was used. For commercial diaper material this value is
served suggesting that the concentration of citric acid may not be 0.293 suggesting that CHCAUR could be a substitute for commercial
adequate enough to be detected by SSNMR. This could be due to the use SAPs used in diapers. The study shows that the water absorption ca-
of basic methanol treatment used to precipitate the product, which may pacity of CHCAUR was about eight times compared to the SAP used in
have dissolved the citric acid present as physical crosslinks in CHCA. In commercial diaper and about 2.5 times that reported earlier by us for
the case of the other control reactions, the SSNMR of CHUR shows all CHEDUR (Narayanan & Dhamodharan, 2015). The higher water ab-
the characteristic peaks of chitosan and one additional peak at sorption capacity of CHCAUR might arise due to the presence of phy-
160.15 ppm, which confirms the presence of urea. sical crosslinks of CAUR connecting the chitosan molecules as shown
The FT-IR spectrum of CHCAUR, CHCA, CHUR, and raw chitosan below.
are shown in Fig. S15 of the Supplementary Material. The FTIR spectra
of CHCAUR and CHCA showed the presence of all the peaks char-
acteristic of chitosan, which suggested that the backbone of chitosan
remained intact following the reactions. The FTIR of CHUR showed an
increase in intensity of the peak at 1560 cm−1 and a new peak at
1115 cm−1, which is attributed to reaction between urea and chitosan
in acid medium to form a urethane bond (NH3-COeOeR; bending vi-
bration of CeOeC urethane bond linked to chitosan) (Lei et al., 2009).
Chitosan repeat unit has one primary alcohol group at C6 and one
secondary alcohol group at C3 position, which can react with urea
under acid medium to form urethane bonds with liberation of am-
monia, which might also be the reason for the increase in pH from 5 to
7.5 after the reaction resulting in ammonia evolution. The increase in
the intensity of 1560 cm−1 peak could be due to the formation of ad-
ditional amide bonds linked to chitosan. The peak at 1115 cm−1 is
absent in CHCA, which confirms the reaction of urea with chitosan in
Fig. 4. Water absorption versus time for CHCAUR, commercial diaper material and
presence of acid. The formation of CHCAUR is also confirmed by
CHCAUR after extraction with sodium hydroxide.
thermogravimetric analysis (Supplementary Material Fig. S16).

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from CHCAUR (Supplementary Material Figs. S18 and S19) suggesting

that CAUR is present as physical ionic crosslinks. The water absorption
capacity of CHCAUR decreased from 1250 g/g to 500 g/g upon this
step, which suggested that 40% of water absorption arises from mor-
phology related effect and the rest was from the physical crosslinks
consisting of CAUR. The SEM image of CHCAUR after extraction with
sodium hydroxide suggested that there was no significant change in
morphology after the extraction of CAUR (Supplementary Material Fig.
S20).
The SEM picture (insert No.7 in Fig. 5) was processed by ImageJ
software. This software is used for calculating the mean pore diameter,
standard deviation and% porosity. The results showed that the
CHCAUR gel mean pore diameter was 0.359 mm and the standard de-
viation was 0.134. The porosity was calculated to be 27.61%.
This structure provides a number of ionic sites by way of charged
The water absorption capacity of CHCAUR could be varied by fine
oxygen and nitrogen atoms in a rigid polymer backbone structure,
tuning the reaction parameters. One such is the quantity of water used
which should also enable higher water absorption by electrostatic hy-
in the preparation of CHCAUR. Upon increasing the quantity of water
drogen bonding in addition to the porous structure of CHCAUR.
with respect to the mass of chitosan (200 mL/g), the water absorption
The higher water absorption capacity could also arise out of the
capacity could be reduced thus enabling the formation of CHCAUR
macro porous structure of CHCAUR. Hence the morphology of CHCAUR
suitable for the preparation of hydrogel.
was assessed by SEM. This confirmed the presence of macro pores
The application of CHCAUR in water conservation was tested by
surrounded by a fibrous network of chitosan molecules forming an
performing moisture retention of soil loaded with CHCAUR. The use of
undulated surface as shown in Fig. 5. The extent of water absorption
super absorbents in agriculture as well as horticulture for water con-
arising out of the presence of physical crosslinks consisting of electro-
servation is known for many years, and many extensive studies have
valent bonds as well as that arising out of the morphology could also be
been reported (Dabhi, Bhatt, & Pandit, 2013). Chitosan, the major
quantitated. Thus CHCAUR was extracted with sodium hydroxide in 1:1
component of CHCAUR, is used in agriculture in seed protection, as
water: methanol followed by repeated rinsing with methanol and dried.
anti-microbial agent, and as disease resistant additive to soil (El
The powder formed in this process confirmed the removal of CAUR
Hadrami, Adam, El Hadrami, & Daayf, 2010). Further, with 11%

Fig. 5. SEM images of CHCAUR at different magnifications − (1) 1 mm (2) 500 μm (3) 200 μm (4) 100 μm (5) 50 μm (6) 10 μm (7) 3 mm. The image generated by ImageJ software and gel
porosity histogram are shown in (8) and (9), respectively.

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Fig. 6. Moisture content in soil versus time, with and without CHCAUR (4 wt%) heated at
35 °C.
nitrogen content, CHCAUR can also serve as a multipurpose material in
agriculture and especially as controlled releasing agent of micro and
macro nutrients to soil. Therefore a detailed study was performed on
the effect of addition of 4% by weight CHCAUR to soil on the water
retention capacity at 35 °C. The result is presented in Fig. 6. The initial
moisture content was 30% for soil with 4% CHCAUR as well as control
(soil without CHCAUR). After 1 h of heating, the soil with CHCAUR
retained 25% of moisture while the control could retain only 10%. After
5 h heating, the control retained only 2% moisture while it took nearly
9 h of heating before the soil with CHCAUR could reach that stage. This
experiment shows that the water evaporation rate from soil is slowed
down considerably in the presence of CHCAUR even at a low dosage of
4%.
These experiments suggested that CHCAUR could find application in
household potted plant growth wherein daily watering is required. Its
application at a predefined level with soil could reduce the number of
watering cycles thereby conserving water. This was observed by us for
the growth of chilly plant (data not shown) wherein a 5% loading of
CHCAUR to soil reduced the frequency of watering to once in every
three days.
5. Conclusion
We report the preparation and characterization of a new super
water absorbent material denoted as CHCAUR, from renewable sources
such as chitosan, citric acid and urea by the hydrothermal synthesis.
CHCAUR was found to absorb a maximum of around 1250 g/g of dis-
tilled water and 210 g/g of 0.1% sodium chloride solution, which is
superior to the absorption of SAP used in Huggies brand baby diaper
material. The water absorption is shown to arise out of the physical
crosslinks consisting of electrovalent bonds, macro pores and morpho-
logical features. CHCAUR is observed to contain a very large proportion
of chitosan and a small proportion of CAUR and therefore it is likely to
biodegrade in soil to a very large extent as observed in preliminary
experiments (results not presented here). CHCAUR when blended with
soil even in low quantity delays the water evaporation from soil.
CHCAUR can be a promising multipurpose soil additive, in view of the
citric acid component, to supply micro and macro nutrients to soil with
controlled release of water.
Acknowledgments
The authors wish to thank the Department of Materials and
Metallurgical Engineering for the electron microscopy facilities and
especially Prof. S. Sankaran. Abathodharanan Narayanan thanks IIT
Madras for enabling him to register for Ph.D. This work was made
possible due to the support of IIT Madras.
159
Carbohydrate Polymers 191 (2018) 152–160
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.carbpol.2018.03.028.
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