Journal Pre-proof

Radiation-synthesized polysaccharides/polyacrylate super water absorbents and their

biodegradabilities

Lorna S. Relleve, Charito T. Aranilla, Bin Jeremiah D. Barba, Alvin Kier R. Gallardo,
Veriza Rita C. Cruz, Carlene Rome M. Ledesma, Naotsugu Nagasawa, Lucille V.
Abad
PII: S0969-806X(19)30310-X
DOI: https://doi.org/10.1016/j.radphyschem.2019.108618
Reference: RPC 108618

To appear in: Radiation Physics and Chemistry

Received Date: 29 April 2019

Revised Date: 22 November 2019
Accepted Date: 24 November 2019

Please cite this article as: Relleve, L.S., Aranilla, C.T., Barba, B.J.D., Gallardo, A.K.R., Cruz, V.R.C.,
Ledesma, C.R.M., Nagasawa, N., Abad, L.V., Radiation-synthesized polysaccharides/polyacrylate super
water absorbents and their biodegradabilities, Radiation Physics and Chemistry (2019), doi: https://
doi.org/10.1016/j.radphyschem.2019.108618.

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 Radiation-synthesized polysaccharides/polyacrylate super water
absorbents and their biodegradabilities
Lorna S. Rellevea,*, Charito T. Aranillaa, Bin Jeremiah D. Barbaa, Alvin Kier R. Gallardoa,
Veriza Rita C. Cruza, Carlene Rome M. Ledesmaa, Naotsugu Nagasawab, Lucille V. Abada
a
Philippine Nuclear Research Institute-Department of Science and Technology
Commonwealth Ave., Diliman, Quezon City, 1101, Philippines
b
National Institutes for Quantum and Radiological Science and Technology (QST)
1233 Watanuki, Takasaki, Gunma, 370-1252, Japan

*Corresponding author: lsrelleve@pnri.dost.gov.ph

Abstract

Different super water absorbents (SWA) based on polysaccharides/poly(acrylic acid) (PAAc)

were prepared by gamma irradiation to be used as soil water retainers. Polysaccharides,
kappa-carrageenan (seaweed and semi-refined forms) and cassava starch were used in the
preparation of SWA to improve biodegradability. Gel fraction of the different SWAs ranged
from 31% to 97% and degree of swelling reached up to about 5890 g H2O/g dry gel. The
physico-chemical and mechanical properties of the SWA were influenced by the degree of
neutralization, macromolecular properties of the polysaccharide and irradiation dose. FTIR
and TGA analyses showed successful incorporation of polysaccharides in the network
structure through formation of covalent bond. Biodegradability test by microbial oxidative
degradation analyzer (MODA) showed that cassava starch/PAAc SWA biodegraded at a rate
of 42% in 85 days compared to 11% of pure PAAc. The cassava starch/PAAc SWAs
retained water up to more than 20 days in sandy soil and still absorbed water after 62 days
with wet/dry cycles in pot experiment.

Keywords: polysaccharides; polyacrylate; gamma irradiation; super water absorbent;

biodegradability;
1. Introduction

Super water absorbents (SWA) can absorb a very large amount of water (many hundred times
their dry weight) and retain it even under pressure. They are synthesized by crosslinking
highly hydrophilic macromolecules. Super water absorbents are used in a wide variety of
applications such as disposable absorbents, in agriculture, and other fields where water
absorption is needed. As soil water retainers or soil conditioners, super water absorbents are
developed to improve the physical properties of soil in view of: (a) increasing their water-
holding capacity, (b) increasing water use efficiency, and (c) increasing plant performance
(Jhury, 1997). Desired features of super water absorbents are high gel content, swelling
capacity, fast swelling and good mechanical strength of the swollen gel. Most of the
superabsorbents available on the market are 100% polyacrylate-based products, therefore not
biodegradable. Biodegradability of super water absorbent is a very important property for
protecting the environment. It has been found that the polyacrylate main chain degraded in
the soils at rates of 0.12-0.24% per 6 months (Wilske et al., 2014). It is the aim of this study
to synthesize biodegradable super water absorbents through the incorporation of
polysaccharides into the polyacrylate structure by radiation methods.

Polysaccharides like starch, carrageenan, cellulose derivatives etc. are good candidate raw
materials for various applications because of their renewability, availability at low cost,
biocompatibility and biodegradability. Kappa-carrageenan is sold commercially as dried
seaweed, semi-refined and refined. The main source of raw material for the carrageenan
industry is Kappaphycus alvarezii, a red alga, widely cultivated in the Philippines. Semi-
refined kappa-carrageenan (SRKC) is used as an alternative for the refined carrageenan
which still contains cellulose as in the original seaweed. It is considerably a cheaper form of
carrageenan. Starch is one of the most abundant substance in nature with unlimited supplies.
Starch is produced from grain or root crops. Cassava is one of the main agricultural crops in
the Philippines. Cassava production in the Philippines has reached 2.806 million metric tons
in 2017 (Philippine Statistic Authority, 2018). About 20% of cassava production is utilized
for starch processing (Bacusmo, 2000).

Radiation technology has emerged as an environment-friendly, commercially viable

technology with broad applications in health, environment agriculture and industry (IAEA-
TECDOC, 2004). This technology is based on the use of ionizing radiation to modify the
structures and properties of materials in different applications. Gamma and electron beam
irradiation are found to be very effective methods for constructing three-dimensional
polymeric networks of super water absorbent. Both offer advantages over conventional
physical or chemical methods of network formation: elimination of need for toxic initiators
and crosslinking agents, mild reaction conditions, negligible by-product formation, fast
gelation and room temperature process. It is easy to control the properties of the materials by
the adjustment of the radiation dose.

In this report, super water absorbents from polysaccharides/polyacrylate were synthesized

and characterized. The gel properties, IR spectra, TG profile, swelling kinetics,
biodegradability and soil water retention and efficiency of the different radiation-synthesized
polysaccharide/polyacrylate-based SWAs are presented. The influence of different
polysaccharides on the gel properties of SWA is discussed.

2
2. Materials and methods

2.1 Materials

Dried seaweed, Kappaphycus alvarezii was obtained from Mioka Biosystem Corporation
Philippines. Semi-refined kappa-carrageenan and refined iota-carrageenan were produced by
Shemberg Corporation Philippines. Cassava starch and carboxymethyl cellulose (degree of
substitution 0.8) were produced by Matling Industrial and Commercial Corporation
Philippines, and CPKelco, Philippines, respectively. Acrylic acid monomer was purchased
from Nippon Shokubai Indonesia. Commercial superabsorbent based on a potassium
polyacrylate formulation, was used for comparison.

2.2 Preparation of SWA

2.2.1 Pure PAAc

Pure PAAc gels were prepared by using an aqueous solution of acrylic acid (AAc) monomer
with a final concentration of 20% w/w. Partial neutralization of acrylic acid was done using
sodium hydroxide until it reached 0, 50 and 75% degree of neutralization (DN). DN refers to
the amount of acrylic acid neutralized in the solution calculated based on mole percentages.

2.2.2 Seaweed/PAAc

Dried seaweed was mixed with deionized water in a reaction vessel and stirred vigorously at
450 rpm for 30 min at 80 °C to form a viscous solution. This is referred to as heat
gelatinization. Temperature was lowered to 60 oC before adding partially neutralized acrylic
acid (25, 50 and 75% DN using NaOH). The slurry was mixed for an additional 15 min. The
final concentration of dried seaweed and AAc in the mixture was 3% and 15-20% w/w
respectively.

2.2.3 SRKC/PAAc

Semi-refined kappa carrageenan (SRKC) based gels were prepared similarly to

Seaweed/PAAc using heat gelatinization, with final concentrations of SRKC and AAc at 3%
and 20% w/w respectively. AAc was partially neutralized with NaOH until DN was 0, 50 and
75%.

2.2.4 Starch/PAAc

The formulation and preparation of Starch/PAAc was adapted from the “Guideline on
development of hydrogel and oligosaccharides by radiation” (FNCA, 2017). Cassava starch
(10% w/w) was gelatinized by heating in water or in alkali solution at room temperature. In
heat gelatinization, AAc (20% w/w) was partially neutralized with potassium hydroxide
(38% DN) before adding to the starch. In alkali gelatinization, starch was first dispersed in
KOH solution (equivalent to 38% DN) at room temperature until it became viscous. AAc
(20% w/w) was then added the mixture and stirred for 30 min. Additional gels were prepared
using heat gelatinization with 20% AAc (50% DN using NaOH) and 3% starch, and with
15% AAc (75% DN using NaOH) and 0-15% starch.

3
2.2.5 CMC/PAAc and IC/PAAc

These gels were prepared using heat gelatinization with final concentration of 3%
polysaccharide with 20% AAc partially neutralized using NaOH until 50% DN.

2.2.6 Irradiation and processing

SWA formulations were poured into plastic pouches, sealed and gamma-irradiated at the
PNRI Irradiation Facility with doses of 15-45 kGy at a dose rate of 0.5 kGy/h. Dosimetry was
monitored using ethanol-chlorobenzene (ECB) dosimetry system following
ISO/ASTM51538-17 standards. The resulting gels were cut into cubes, air-dried and oven-
dried at 50 oC for 24 h. Samples were further ground to granules (1-3 mm) for evaluation of
swelling kinetics, biodegradation and soil-water retention.

2.3 Characterization of gel properties of SWA

2.3.1 Gel fraction (GF) and degree of swelling (DS)

The degree of swelling of the SWA was determined by gravimetric method, adapted from
(Al-Assaf et al., 2016) with some modification. SWA samples (about 0.2 g) dried to a
constant weight were immersed in 1 L of deionized water at room temperature for 7 days to
ensure maximum swelling, i.e. swelling values plateaus and no longer changes. Water was
changed daily. The swollen gel samples were periodically weighed after removing the surface
water with a tissue paper. After 7 days, the swollen samples were removed from the water
and dried to constant weight to get the gel fraction. The gel fraction and degree of swelling
were calculated as follows:

Gel fraction: (%): =

Degree of swelling =

where Wd is the weight of dried insoluble part after immersion for 7 days, Wi is initial weight
of dried sample after irradiation and Ws is the maximum weight of swollen gel. All
measurements were done in triplicates.

2.3.2. Gel strength (GS) of swollen SWA

Dry gels were immersed in water for 24 h or until it absorbed 100 g of water per gram of
dried gel. Compression test using the Zwick Roell Universal Testing Machine was carried out
on the swollen gel using a 10 mm-diameter stainless steel probe at a crosshead speed of 3
mm/min.

2.3.3. Swelling kinetics

Selected SWA formulations were ground to 1-3 mm granules and immersed in deionized
water. The gels were weighed by filtering through a stainless-steel sieve (200 µm). The
sample was immersed again in water and the procedure was repeated for different swelling
times. The DS at different swelling time was calculated using equation in Section 2.3.1.
4
2.4 FTIR analysis

SWA samples were washed extensively by immersing them in deionized water for 7 days,
with frequent change in water, in order to extract sol fraction. The gels were then dried and
subjected to FTIR analysis. The infrared spectra (600-4000 cm-1) were examined by a Perkin
Elmer Spectrum One FTIR spectrophotometer in attenuated total reflectance (ATR) mode
with a resolution of 4 cm-1.

2.5 Thermogravimetric analysis

As with FTIR analysis, SWA samples were washed extensively and dried before subjecting it
to thermogravimetric analysis. Thermal decomposition properties of the SWA samples (~10
mg) were investigated using a Netzsch STA449 F3 Jupiter over the temperature range of 25-
1000 °C with a heating rate of 10 °C/min under nitrogen atmosphere.

2.6 Biodegradation test

The biodegradation test was done in the laboratory of National Institutes for Quantum and
Radiological Science and Technology, Takasaki, Japan. The microbial biodegradability of the
super water absorbents was evaluated by measuring released carbon dioxide (CO2) using the
Microbial Oxidative Degradation Analyzer (MODA) (Saida Ironworks Co., Ltd). The scheme
of MODA is shown in Fig. 1. The test was performed as previously described (Nagasawa et
al, 2004). Briefly, 5 g of the sample (dry granules) was mixed well with 320 g of rinsed sea
sand, 60 g of compost and 95 g of water. This was then placed in the heated reaction column.
The temperature inside the reaction column was maintained at 35°C. Moisturized air (CO2
free) was flowed through the sample inside the reactor and the flow rate was kept at 30
ml/min. The air carrying CO2 (formed due to polymer decay) that flowed out of the reactor
was passed through a series of columns. Ammonia, which could be formed from the
decomposing sample, was trapped in sulfuric acid solution and water vapor was absorbed
into the first two columns (silica gel and calcium chloride). The CO2 was collected
quantitatively by soda lime while water generated during the reaction was trapped in the last
calcium chloride column. The amount of produced CO2 was calculated as a difference in the
weight of two last columns (containing soda lime and calcium chloride) at the beginning and
during the testing period. Pure compost mixed sea sand was used as a blank sample and
cellulose powder as a reference sample. Biodegradation was calculated as indicated below:

% Biodegradation =

2.7 Soil water retention and efficiency

Four hundred grams of dry sandy soil (1:1 garden soil:sand) were placed in plastic pots. Soil
was taken from the PNRI vicinity. SWA samples in the concentration range of 0.25-1%
(based on the weight of soil) were applied as either dry granules mixed with the soil or as
pre-swollen gels arranged in between layers of the soil. Set-ups without SWA and with
commercial product were used as controls and reference, respectively. Each pot was initially
wetted with 600 mL (dry granules) or 300 mL (pre-swollen gels) of water. Pots were
rehydrated with 400 mL of water roughly every two weeks and weighed after allowing the
set-ups to drip for one day. Pots were weighed daily for a period of 53 days. Water content
was calculated as:
5
 Water content (%) =

2.8 Statistical analysis

Data was evaluated using GraphPad Prism 8. Numerical data are presented as mean values ±
standard deviation when applicable. Means of different treatment groups/parameters/samples
were analyzed using ANOVA including post-tests such as Bonferroni test. Values were
considered significant at p<0.05.

3. Results and Discussion

3.1. Radiation crosslinking of poly(acrylic acid) in aqueous solution

Formation of poly(acrylic acid) super water absorbent gel in this study using radiation
involved the polymerization of acrylic acid monomer followed by crosslinking interactions.
Free radical polymerization of acrylic acid monomers can be initiated to form homopolymers.
Ionizing radiation leads to the formation of vinyl radicals that propagates with addition of the
vinyl monomers (Reaction 1). A key advantage of radiation-induced polymerization is that it
has lower activation energy which translates to high conversion rate. The covalent bonds of
water and PAAc dissociates causing the formation of radicals. Radiolysis of water molecules
produces hydrated electrons (eaq-), hydroxyl radicals (HO·) and hydrogen radical (H·)
(Reaction 2). Likewise, the C-H bond of ionized PAAc breaks, then a polymer radical and a
hydrogen radical are formed in Reaction 3. Radical transfer reactions between PAAc and
hydroxyl and hydrogen radicals dominate to form polymer radicals. These polymer radicals
recombine causing gel formation. As monomers are converted to polymers, polymer buildup
occurs. With continuous radiation exposure, these polymers can be reactivated which leads to
the formation of branched polymer molecules, such that remaining monomers can be
“homografted” to its own polymer. When conversion reaches very high values, crosslinked
gels can be formed (Adolphe Chapiro, 1979). The most important reactions of radiation
crosslinking of PAAc in aqueous solution as described by Jabbari and Nozari (2000) are
shown from Reaction 4 to 7.

AAc → PAAc (1)

H2O → H·, HO·, eaq-, H2, H2O2, H3O+ (2)

PAAcH → PAAc· + H· (3)

PAAcH + (H· or HO·) → PAAc· + HOH or H2 (4)

PAAc·m + PAAc·n → PAAcm‒PAAcn (5)

PAAc·m+n → PAAcm + PAAc·n (6)

PAAc·m+n + O2 → PAAcm+n‒O2· (7)

→ PAAcm‒C(O)H + PAAcn‒O·

6
Reaction (4) involves the reaction of the HO· and H· radicals with poly(acrylic acid) by H-
abstraction at the α and ß-positions to the carboxylic acid. Most ß-macroradicals of PAAc are
converted α-macroradicals by rearrangement (Ulanski et al., 1996). In reaction (5), it is the
pathway for increasing the gel formation. In reaction (6), polymer degrades and in reaction
(7), molecular oxygen present reacts with polymer radical to give a decomposition product,
aldehyde.

3.2. Radiation synthesis of polysaccharide/PAAc SWA

An important feature of super water absorbent, especially when used in agricultural

application, is its biodegradability. This ensures that the product remains eco-friendly and
reduces pollution contribution. While the market is dominated by polyacrylate-based SWA,
increasing environmental awareness has shifted the demand to biodegradable SWA, usually
achieved by a blend of natural polymers such as polysaccharides. This reduces reliance on
petroleum-based, nonrenewable resources while producing sustainable, environment-friendly
and nontoxic products.

The process of preparing polysaccharide-polyacrylate blend super water absorbents involves

first the gelatinization of the polysaccharide in order to fully extend their chains and improve
dissolution and mixing. This is achieved by either heat or alkali treatment under shear stress.
The heat or base added breaks down intermolecular association of polysaccharide molecules
allowing hydrogen bonding with water. High shear forces, on the other hand, allows for faster
diffusion of water into the polysaccharide network by physical tearing apart its granules and
reducing its crystallinity (Burros, Young, & Carroad, 1987; Wen, Rodis, & Wasserman,
1990). Another component in the process involves neutralization of the carboxylic groups of
the acrylic acid component. This replaces H+ with Na+ or K+ with the addition of the
corresponding hydroxide base. Upon contact with water, these ions are hydrated which
reduces their attraction to the carboxylate ions and allows the Na+ or K+ ions to move more
freely inside the network. This contributes to the osmotic driving force for the diffusion of
the water into the gel (Witono et al., 2014). Neutralization is done before or after crosslinking
for optimum swelling or absorbency (Francis et al., 2004, Sutradhar et al., 2015, Wang et al.,
2010, El‐Mohdy et al., 2007, Bhuyan et al., 2016). In this study, neutralization was done
before crosslinking for easier processing.

As in the radiation synthesis of PAAc gels, polysaccharide/PAAc SWA was subjected to

gamma irradiation simultaneously. The bulk of the reactions occurring in the mixtures of the
polysaccharide and acrylic acid monomer are mediated by species formed from the radiolysis
of water molecules. Reactive species (hydrated electrons, hydroxyl radicals and hydrogen
atoms) can give rise to several possible mechanisms within the mixture as summarized in Fig.
2. Abstraction of hydrogen on the polysaccharide backbone can form macroradicals on its
surface, which can lead to chain scission (a), especially at oxygenated solutions; various
transformations of the sugar units (b) (G. Ershov, 1998); or these radicals can serve as graft
points for the polymerization of acrylic acid (c) (Mittal, Ray, & Okamoto, 2016).
Polymerization and crosslinking mechanisms of acrylic acid discussed in the previous section
may also occur in the mixture (d) as well as recombination of macroradicals between either
the polysaccharide, chain scission products or polyacrylic acid chains (e) (Al-Assaf et al.,
2016; Makuuchi, Yoshii, Aranilla, & Zhai, 2000). While it is difficult to fully elucidate the
nature of the reactions within the mixture and which mechanisms predominate, the properties
exhibited by the synthesized hydrogels suggest the formation of a three-dimensional network
7
resulting from significant crosslinking. Graft copolymerization, while a possible mechanism,
is much more difficult to elucidate, though several studies use this term liberally (El-mohdy,
Hegazy, & El-rehim, 2006; Kiatkamjornwong, Chvajarernpun, & Nakason, 1993). Another
mechanism that has also been suggested is noncovalent, physical entanglement of gelling
type polysaccharides to the crosslinking polymer (PAAc) to form a interpenetrating network
(Abad, Relleve, Aranilla, & Dela Rosa, 2003; Jing, Yanqun, Jiuqiang, & Hongfei, 2001). The
properties of radiation-synthesized pure PAAc and polysaccharide/PAAc SWAs are
presented in succeeding discussions.

3.2.1 Pure PAAc

Table 1 presents the crosslinking of PAAc with 20% AAc concentration at different DN.
PAAc gels with 0% DN had almost 100% gel fraction. Partial neutralization of acrylic acid
showed some decrease in gel fraction especially at 75% DN. Several studies noted that there
is less recombination of macroradicals at higher pH due to electrostatic repulsion of polymer
chains (Ulanski and Rosiak, 1994, Zhu et al., 1998). Poly(acrylic acid) acts like a
polyelectrolyte with a pKa value of ~6.2 (Oosawa, 1971). Below pKa, carboxylic acid groups
are predominantly undissociated. Above pKa, PAAc chains are ionized and can adapt a stiff
and extended conformation due to repulsion of the negative charges of the carboxylate
species. For radical recombination of neighboring chains to occur, these repulsive forces
must first be overcome. Prior to irradiation, pH values of the acrylic acid solution were 2.2,
5.01 and 5.85 at 0, 50 and 75% DN, respectively. These values correlate well with the
observed trend in gel fraction. At pH 5.85, it approaches the pKa of PAAc wherein more
carboxylic groups are ionized that caused the gel fraction to decrease at 75% DN. Swelling
capacity, on the other hand, increased with increasing DN. Expectedly, higher swelling
values were obtained from gels with lower gel fractions due to less restriction of the hydrogel
network. Low osmotic diffusion may also be observed when carboxylic acid groups are less
ionized, as with low DN (Bhuyan et al., 2016, Fekete et al., 2016). While 50% DN gels may
offer a good balance of sufficient crosslinking and swelling capacity, poor biodegradability of
acrylate-based gels remains a significant constraint in its utilization as superwater absorbents
in agricultural applications. Incorporation of natural polymers like polysaccharides were
explored as an alternative.

3.2.2. Seaweed/PAAc SWA

Acrylic acid solutions with 15% and 20% concentration were investigated for the preparation
of seaweed/PAAc super water absorbent, as previous study reported this concentration range
produced SWA with good properties (Sanju et al., 2004; FNCA Guideline, 2017). The results
are summarized in Table 2. At 25-50% DN, the gel fraction ranged from 31 to 85%. The
amount of gel fraction measured gives stability to the SWA since it will be able to retain or
hold water at a higher degree without simply leaching out in the soil when used as water
retainer. Gel fraction was found to increase with decreasing DN (p<0.05), similar to pure
PAAc gels. Notably, samples with 15% AAc at 75% DN did not form gels even at absorbed
dose of 45 kGy. The pH of this solution before irradiation was 5.2, which approached the
pKa of PAAc of ~6.2. This is also above the pKa of the main component of the seaweed-
kappa-carrageenan (~2). Both groups, -COOH and -OSO3H of kappa-carrageenan are mostly
ionized at this pH and therefore they have extended conformation. Greater repulsive force
between these ionized groups prevents polymer radicals from recombining and competitive
8
reactions, such as chain scissions, proceed with higher probability as charge density increases
(Sakurada & Ikada, 1963). The 15% AAc alone at this DN also did not form gels as will be
shown in the later section. This was also observed in the study by Lappan & Uhlmann (2010)
on PAAc crosslinking in dilute solutions, wherein no gelation was observed when initial pH
was greater than 5. Meanwhile, seaweed/PAAc using 20% acrylic acid formed gels at 75%
DN. Here, the increased concentration limits the spacing between the mixture components
and forces the polymers to come together, enough to overcome charge repulsion and lead to
network formation with gel fraction of 31-33%. This remains significantly lower than
samples at lower DN. There is less electrostatic inhibition of crosslinking at lower DN as
discussed earlier.

All gel fractions recorded for this formulation are evidently lower than that of pure PAAc,
owing mostly to the filler effect of the added polysaccharide which competes with PAAc for
the free radicals. On the other hand, the addition of the hydrophillic polysaccharide improved
the swelling capacity of the gels and loosens the 3D network for better water absorption and
stress transfer. The swelling capacity of seaweed/PAAc SWA with 25-75% DN (15-45 kGy),
ranged from 347 to 5890 g H2O/g dry gel and gel strength of 1-10 kPa. Among the samples in
this formulation, 25% DN was found to be suitable for the preparation of
seaweed/polyacrylate SWA as it had higher gel fraction accompanied by acceptable degree of
swelling especially at lower doses.

3.2.3 Semi-refined kappa-carrageenan/PAAc SWA

The characteristics of SWA made from SRKC/PAAc are presented in Table 3. The
SRKC/PAAc SWA had gel fractions in the range of 62-78% at 50-75% DN and absorbed
doses of 15-30 kGy. There was an appreciable crosslinking as indicated by an increased gel
fraction even at 75% DN and 15 kGy as compared to seaweed-based-SWA. While the major
component of Kappaphycus alvarezii is KC, there may be some residual amount of proteins,
fats and minerals in the unprocessed seaweed, along with phenolic bioactive components that
could reduce the efficiency of the radiation process (Prabha, Prakash, & Sudha, 2013).
SRKC, on the other hand, has gone through extraction processes that remove these impurities
such that it is mostly comprised of only KC and a small amount of cellulose (McHugh,
2003).

The gel fraction still increased with decreasing degree of neutralization like with seaweed-
based SWA and pure PAAc. The SRKC/PAAc with 0% DN exhibited high gel fractions (95-
97%) compared to the partially neutralized SWA. In addition, at 20% AAc and 50-75% DN,
both SRKC/PAAc and seaweed/PAAc had lower gel fraction compared to the pure PAAc
while at 0% DN, SRKC/PAAc and pure PAAc had almost the same gel fraction. Thus, higher
percentage of SRKC was incorporated when AAc was unneutralized. This could be attributed
to the acid effect. Prior to irradiation, pH level of 0% DN sample was found to be 2.9. In
acidic solutions, there is less electrostatic inhibition of crosslinking and the presence of H+
can increase G(H•) and encourages abstraction of hydrogen preferentially from saturated
organic molecules (A Chapiro & Dulieu, 1977; Suda Kiatkamjornwong & Meechai, 1997).
Recombination of these radicals can form T type molecules when KC chain attaches to PAAc
or H type molecules from recombination of PAAc chains (Makuuchi et al., 2000).
Furthermore, if the polymerization/crosslinking of acrylic acid and the degradation of the
polysaccharide occurred separately, the maximum gel fraction for the 0% DN should be 87%.
However, gel fraction was recorded at 95-97% even after extensive washing of sol fraction.
9
SRKC in this condition was effectively incorporated into the gel either by crosslinking or
grafting mechanisms (Abad et al., 2003).

The degree of swelling ranged from 556 to 1693 g H2O/g dry gel for SRKC/PAAc SWA gels
at 50% and 75% DN and with doses of 15-30 kGy. The swelling of SRKC/PAAc SWA with
0% DN were rather very low with values of 29-71 g H2O/g dry gel. Unneutralized gels of
CMC/PAAc and potato starch/PAAc were reported also to have low degrees of swelling due
to low osmotic diffusion when carboxylic acid groups are less ionized (Bhuyan et al., 2016,
Fekete et al., 2016). This type of SWA may not be useful in agricultural or hygiene products
due to low water absorption.

3.2.4. Cassava starch/PAAc SWA

The formulation of cassava starch/PAAc SWA, as adapted from the FNCA guidelines, was
20% acrylic acid, 10% starch and 38% degree of neutralization (solution pH measured at
4.78). In the synthesis process, the gelatinization of starch can be achieved by heating with
water or mixing with alkali solution at room temperature. Table 4 gives the gel properties of
the cassava starch-based SWA. Gel fraction, degree of swelling and gel strength were all
significantly higher in alkali gelatinization, especially at doses 20-25 kGy (p<0.05). Thermal
gelatinization involves the thermal disordering of crystalline structures in native starch
granules. Once heated past its gelatinization temperature, typically between 57-65 °C,
hydrogen bonding of starch molecules is disrupted, and water molecules become attached to
their hydroxyl groups which leads to greater swelling and dissolution (Liu, Xie, Yu, Chen, &
Li, 2009). On the other hand, in alkali treatment, the base ions disrupts the hydrogen bonding
by deprotonation accompanied by some physico-chemical changes on the starch structure
(Ragheb, Abdel-Thalouth, & Tawfik, 1995). Because of ionic interactions and
transformations, alkali treatment seemed to be more effective in the gelatinization process
and yielded better results than simple heat gelatinization.

Pure PAAc synthesized using the same conditions (20% AAc, 38% DN, 15 kGy) had the
swelling capacity and gel strength of 1076 g H2O/g dry gel DS and 39 kPa, respectively. The
swelling of pure PAAc was much greater than that of SWA containing heat or alkali-treated
starch but had lesser gel strength. These characteristics of SWA suggested incorporation of
starch in the gel network. In addition, if only PAAc formation in the gel is accounted for, gel
fraction should be at around 70% if full conversion was achieved. However, starch-based
SWA had higher gel fractions ranging from 80-94% and so starch molecules must be
effectively incorporated in the SWA such that they were retained despite sol extraction.

The behavior of cassava starch/PAAc fixed at only 15% AAc and 75% DN with varying
starch concentration and doses of 15-45 kGy was also studied and presented in Table 5. No
gels were obtained at 0-5% starch and these results are similar to seaweed/PAAc. At higher
starch concentrations of 10-15%, substantial gel fractions in the range of 42-61% were
obtained. This highlights the importance of sufficient starch concentration in the SWA
formation. Possibly, increase in the total substrate concentration pushed the reactants in close
proximity enough to form covalent bonds despite charge repulsion between polymer chains at
relatively higher pH.

10
3.3. Influence of different polysaccharides on the gel properties of SWA at fixed conditions

Fig. 3 shows the effect of different polysaccharides, CMC, SRKC, IC and cassava starch, on
the gel properties of PAAc SWA with fixed polysaccharide and AAc concentrations, and DN,
i.e. 3% polysaccharide, 20% AAc and 50% DN. As seen in the figure, both carrageenan-
based SWAs synthesized at 15 kGy absorbed large amounts of water compared to other
polysaccharide-based SWAs. The presence of sulfate groups in carrageenan may have led to
the increased degree of swelling. Presence of charges within the SWA causes an osmotic
pressure difference between the gel and water and creates a driving force that diffuses the
solvent into the gel. This effect can be tapered by increasing crosslinking density as a
function of dose, which limits diffusion and expansion. The difference in the gel fraction of
KC and IC-based SWAs, though similar in sugar structure, is probably due to differences in
charge density and gelation mechanism. IC is more sulfated than KC, and has a greater
charge density of 1.49 per disaccharide while KC is at 0.96 (Hugerth, Caram-Lelham, &
Sundelöf, 1997). While helpful in aiding in swelling, the negative charges impede radical
recombination during crosslinking. Moreover, their gelation mechanism generally follows the
transition from random coils to helix formation. In KC gels, the double helices further
associate together and this mechanism aids in the formation of tightly bound interpenetrating
network between KC chains and PAAc. IC, on the other hand, only form double helices
without association, such that any non-covalently bonded chain may get extracted during
washing (Thomas, 1997). CMC/PAAc had the highest recorded gel fraction, owing possibly
to the additional crosslinking capability of its carboxymethyl groups (Kume, Nagasawa, &
Yoshii, 2002). This may also explain its comparatively low swelling and high gel strength
despite also having a relatively high charge density (~1.11). Starch-based gel had lower
swelling than the other polysaccharides especially considering it has the lowest gel fraction.
Unlike the carrageenans and CMC, starch is a neutral molecule with high pKa at 12.6
(Bertolini, 2009). At fixed DN for all polysaccharides with initial mixture pH at ~4.9, only
starch-based gels are non-ionized and lack the extra charges that facilitate osmotic water
absorption. The gel strengths of the different followed the order of CMC > starch >
carrageenan. CMC leads because of its relatively higher crosslinking density (gel fraction)
while extensive hydrogen bonding and rigidity of starch granules translate to better gel
strength despite lower gel fraction (Lin, Liang, & Chang, 2016). Carrageenans, on the other
hand, form relatively weak gels (Thomas, 1997).

3.4. FTIR and TG analyses

Characterizations were done on the representative samples from the different

polysaccharide/polyacrylate-based SWA to check for its composition after sol extraction.
Conditions were fixed at 3% polysaccharide, 20% AAc, 50% DN and 15 kGy dose.

FTIR spectra are shown in Fig. 4. Pure polysaccharides show distinctive peaks at 3400, 2920
and 2850, and 1100-950 cm-1 corresponding to O-H, C-H and C-O stretching of sugar units.
Pure PAAc, on the other hand, show unique peaks at 1700 and 1560 cm-1 due to carboxylic
and carboxylate groups of the polymer. As expected, all gel fractions exhibited peaks from
acrylic acid indicating presence of polyacrylic acid in the gel. PAAc also exhibits absorption
peaks which coincide with polysaccharide peaks, which made it difficult to distinguish.
However, PAAc only has weak absorption at 1100-950 cm-1 but some of the gels, particularly
SRKC/PAAc, starch/PAAc and CMC/PAAc, showed more intense peaks at this region
indicating successful incorporation of the polysaccharide.
11
The thermograms of the SWA gel fractions and their components are shown in Fig. 5. The
thermal degradation profile of pure PAAc occurred in three steps, (i) dehydration at less than
200°C, which is also the general first step for all the other samples; (ii) decarboxylation and
loss of small molecules (e.g. H2O, CH4, etc.) at 200-330°C; and (iii) chain scission and
depolymerization at greater than 350°C. Broad DTG peaks at the second and third
decomposition stage may have been due to the different chain lengths formed during PAAc
homopolymerization (Calahorra, Cortázar, Eguiazábal, & Guzmán, 1989; Nishizaki &
Yoshida, 1981). The Tmax indicated by the DTG peak was at 453°C. This is slightly higher
than the Tmax of PAAc in literature, usually at 380-410°C (Bin-Dahman, Jose, & Al-Harthi,
2015; Dubinski, Grader, Shter, & Silverstein, 2004; Jose, Shehzad, & Al-Harthi, 2014),
suggesting additional thermal stability which may have been caused by crosslinking.

The main decomposition of seaweed was at 150-207°C. The seaweed-PAAc generally

follows the thermogram of pure PAAc, indicating that the gel was made primarily of only
PAAc. The same goes for IC which decomposes mainly at Tmax 232°C but whose gel
generally follows that behavior of pure PAAc. SRKC, on the other hand, was found to start
its main decomposition at 188°C with Tmax at 212°C. SRKC/PAAc also exhibited a small
decomposition Tmax at 178°C suggesting possible grafting of SRKC. Grafted polysaccharides
typically exhibit lower thermal stability than pure polysaccharides due to free volume effects
(Athawale & Lele, 1998; Tanodekaew et al., 2004) . The same trend could be seen for starch-
AAc and CMC-PAAc whose Tmax shifted from 310°C to 305°C and 285°C to 256°C
respectively. The results from both FTIR and TG indicate possible grafting of AAc onto
SRKC, starch and CMC but not on seaweed and IC. Again, other residues found in seaweed
and the higher charge density of IC may obstruct their participation in the grafting or
crosslinking of the SWA hydrogel.

3.5. Biodegradability

Biodegradability, which is a desired characteristic of super water absorbent, is the ability of a

material to be converted into CO2 through the action of microorganisms such as bacteria,
fungi, and algae. Despite the impressive characteristics of polyacrylate SWA, its low
biodegradability, typically less than 1% rate of degradation in soil per six months, has been a
significant setback in its utilization (Wilske et al., 2014). This has been the driving force in
the research for amended SWA formulations that can integrate the usefulness of polyacrylate
SWA with acceptable biodegradability. Incorporation of water absorbing natural polymers
like polysaccharides has been the attractive option.

Biodegradation was studied using MODA, which has been demonstrated to be an effective
test method for determining the ultimate biodegradability of plastic materials (Hoshino et al.,
2007). Weight loss method cannot accurately determine a degree of biodegradation over
70%, because the remnants of materials that have already degraded to 70% cannot be totally
recovered (Kunioka et al., 2009). Furthermore, the advantage of using MODA over
conventional soil burial test is that degradation is measured as the byproduct of microbial
processing without ambiguity. Soil burial test can often mistake run-off of low molecular
weight fragments as full degradation.

12
To evaluate the improvement of biodegradability of the polyacrylate SWA with the
incorporation of polysaccharides, biodegradation tests by MODA were carried out.
Formulations tested were the following: (a) 10%starch/20%AAc at 38% DN and 15 kGy
prepared by heat method (S/PAAc); 3%SRKC/20%AAc at 50% DN and 15 kGy
(SRKC/PAAc); and (c) 20%AAc at 50% DN and 15 kGy (Pure PAAc). The samples were
tested without extraction of sol fraction in order to simulate real-world application which
eliminates the extraction step for convenient and economical processing. Results of
biodegradation tests after 85 days in the controlled compost are shown in Fig. 6. The control
used was cellulose which showed around 10% biodegradation within 3 weeks and a steady
incremental increase henceforth. This slow degradation could be attributed to the crystalline
structure of cellulose. Polysaccharide-based SWA showed an initial biodegradation curve at 3
weeks which could be attributed to polysaccharides trapped within the crosslinked network
(as in an interpenetrating gel model). Afterwards, a steady and fast increase was observed
with S/PAAc. The SRKC/PAAc, on the other hand, had low biodegradation rate (12.9% in 85
days). This may have been caused by the acidification of the compost resulting from the
sulfate that was released after biodegradation of unbound SRKC in the first few days of
incubation and could cause inhibition of the microbial activity. Similarly, the commercial
product had negative values of CO2 which suggest possible toxic effect of the sample and/or
its degradation products on the microbes in the compost. Among the SWA tested, the
cassava starch-based SWA had the highest biodegradability with a rate of 42% in 85 days
compared to pure PAAc with a rate of 11%. The biodegradation of pure PAAc may be due to
the low molecular-weight fragments from the soluble fraction which are more susceptible to
microbial degradation. The incorporation of starch induced by radiation processes resulted in
higher biodegradation rate of the SWA which is useful for environment friendly SWA
products.

3.6. Swelling rate

The swelling rate is one of the important characteristics of a super water absorbent for
hygiene products, agricultural and other applications. For example, the SWA should quickly
absorb water upon irrigation of soil. For swelling of hydrogels, it may be expressed by the
following equation:
t/DS = A + Bt

where DS is the degree of swelling at time t, B =1/DSeq is the reverse of the equilibrium
swelling or A = 1/(ksSeq2) is the reciprocal of the initial swelling rate of the gel and ks is the
swelling rate constant. The initial rate of swelling, theoretical equilibrium swelling, and
swelling rate constants are presented in Table 6. The values of theoretical equilibrium
swelling were relatively in good agreement with the values obtained experimentally. The
initial swelling rate (ri) is the velocity before the networks are strained and begin to retard
swelling. The initial rate of swelling of commercial SWA was comparably higher than the
radiation-processed SWAs. The swelling rate of the radiation processed super water
absorbents needs to be improved. Swelling rate of the super water absorbents was found to be
related to the porosity of the network. A rapid swelling superporous hydrogel (SPH) has been
synthesized through the gas blowing technique by acid decomposition of bicarbonates (Sanju
et al., 2009, Chavda et al., 2012). It has been shown that the presence of interconnected
microscopic pores makes SPHs absorb water very rapidly and swells to equilibrium in a short
period. This process could be integrated into the current method of preparation of SWA.

13
3.7. Soil water retention and efficiency of cassava starch/polyacrylate SWA

Based on the data obtained, cassava starch-based SWA appears to be an ideal SWA material
for agriculture due to its biodegradability, gel properties, and low cost. The soil water
retention properties of S/PAAc were characterized. Fig. 7 shows the soil water retention of
S/PAAc at different application rate (applied as dried granules) in sandy soil. As expected,
the water holding capacity of soil was found to increase with the concentration of SWA. The
starch-based SWA can increase the water content to 92%, 76%, 61% and 48% with the
addition of 1%, 0.75%, 0.50% and 0.25% SWA, respectively. The water content of the
control (without SWA) was 38%. In the soil with 1.0 % SWA, the amount of water was still
50% even after 16 days while soil with 0.75% and 0.5% SWA had only 25% and 18%
retention, respectively. For the soil without SWA and with 0.25% SWA, almost no water was
present after 16 days. Thus, an application rate in the range 0.5-1.0% could be effective.

Efficiency of water retention of starch-based SWA was evaluated by extending to longer

incubation period with wet/dry cycles. Fig. 8 shows the water retention pattern for 62 days of
S/PAAc and commercial product in sandy soil. In the first cycle or first rehydration (day 21),
water absorption of the S/PAAc-amended soil decreased from 80% to 53% and decreased
further to 39% after third cycle. The commercial SWA was relatively stable during the 34-
day incubation period as demonstrated by the consistent value of water content at each cycle.
These results showed that the SWA crosslinked at 15 kGy was not efficient as it loses its
water retention properties on day 34 (i.e. its water content almost similar to the control) while
the S/PAAc-20 kGy SWA had still the capacity to absorb 53% water content after 62 days.
These differences in results could be due to different crosslinking density or due to difference
in cation exchange from the soil. Studies on further optimization of properties of cassava
starch-based SWA and the cause of loss of efficiency will be reported on our next
publication.

4. Conclusions

Different super water absorbents were prepared from different polysaccharides and acrylic
acid by simultaneous gamma irradiation. SRKC/PAAc, starch/PAAc and CMC-PAAc were
successfully synthesized as proven by gel fraction, FTIR and TGA analyses. Important
considerations in the synthesis of SWA with good properties include gelatinization of
polysaccharide, with alkali method proving to be more effective, and partial neutralization of
acrylic acid which encourages radical recombination and creates osmotic force for swelling.
Biodegradation test supports the improvement of biodegradability of acrylate-based-SWA
with the incorporation of starch. Cassava starch-based SWA appears to be a promising SWA
material for agriculture due to its biodegradability, gel properties, and low cost.

Acknowledgements

The authors thank Dr. Jordan F. Madrid and Mr. Patrick Jay E. Cabalar of Philippine Nuclear
Research Institute for helpful discussions and Mr. John Andrew A. Luna for his experimental
assistance. They are also grateful to National Institutes for Quantum and Radiological
Science and Technology for allowing biodegradation studies to be conducted in their
laboratory.

14
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17
 Table 1. Gel properties of pure PAAc super water absorbent with different degree of
neutralization (20% AAc).

Dose GF (%) DS (g H2O/g dry gel) GS (kPa)

(kGy) 0% DN 50% DN 75%DN 0% DN 50% DN 75% DN 0% DN 50% DN 75% DN
15 100 ± 2 94 ± 3 87 ± 4 30 ± 2 845 ± 63 2094 ± 343 1061 ± 3 15 ± 6 4.2 ± 3.6
30 97 ± 1 98 ± 2 90 ± 3 26 ± 4 454 ± 9 1175 ± 76 474 ± 78 9±1 3.7 ± 0.8
The pH of solutions with 0%, 50%, and 75% DN were 2.20, 5.01, and 5.85, respectively. Gel strength at 24 h
swelling

Table 2. Gel properties of seaweed/PAAc super water absorbent with different concentration of
AAc and degree of neutralization (3% seaweed, 15-20% AAc)

GF (%) DS (g H2O/g dry gel) GS (kPa)

AAc Dose
(%) (kGy) 25%
50% DN 75%DN 25% DN 50% DN 75% DN 25% DN 50% DN 75% DN
DN
15 80 ± 4 31 ± 12 -- 840 ± 88 5890 ± 1405 -- 3.9 ± 0.7 nd --
15 30 85 ± 2 61 ± 13 -- 531 ± 75 2144 ± 449 -- 4.3 ± 1.5 1.1 ± 0.2 --
45 81 ± 2 53 ± 1 -- 347 ± 24 1893 ± 51 -- 9.5 ± 2.4 2.0 ± 0.4 --
15 70 ± 2 56 ± 3 33 ± 3 1426 ± 151 1527 ± 385 4522 ± 622 5.7 ± 1.1 3.2 ± 0.2 nd
20
30 70 ± 2 60 ± 2 31 ± 15 1035 ± 160 1055 ± 26 4177 ± 2776 7.8 ± 0.7 5.1 ± 0.5 nd
The pH of solutions from 15% AAc, with 25%, 50%, and 75% DN were 4.19, 4.70, and 5.20, respectively.
The pH of solutions from 20% AAc, with 25%, 50%, and 75% DN were 4.47, 5.08, and 5.91, respectively.
Gel strength at 24 h swelling
“--” no gel formation; “nd” no data (below detection limit); means between varying DN are significantly different
(p<0.05)

Table 3. Gel properties of SRKC/PAAc super water absorbent with different degree of
neutralization (3% SRKC, 20% AAc)

Dose GF (%) DS (g H2O/g dry gel) GS (kPa)

(kGy) 0% DN 50% DN 75%DN 0% DN 50% DN 75% DN 0% DN 50% DN 75% DN
15 97 ± 2 72 ±7 62 ± 2 71 ± 17 1357 ± 449 1693 ± 103 186 ± 3 1.0 ± 0.3 nd
30 95 ± 2 78 ±2 74 ± 2 29 ± 5 556 ± 34 1174 ± 83 313 ± 5 6.0 ± 1.8 nd
The pH of solution with 0%, 50%, and 75% DN were 2.88, 4.87, and 5.38, respectively. Gel strength at 24 h swelling
“--” no gel formation; “nd” no data (below detection limit; means between varying DN are significantly different
(p<0.05)
Table 4. Gel properties of cassava starch/PAAc super water absorbent (10% starch, 20% AAc, 38%
DN)
Heat Gelatinization Method Alkali Gelatinization Method
Dose
GF DS GS GF DS
(kGy) GS (kPa)
(%) (g H2O/g dry gel) (kPa) (%) (g H2O/g dry gel)
15 80 ± 14 182 ± 37 100 ± 20 93 ± 2 194 ± 3 110 ± 22
20 80 ± 1 95 ± 5 43 ± 17 92 ± 1 183 ± 11 94 ± 37
25 94 ± 4 87 ± 6 74 ± 14 93 ± 1 165 ± 5 133 ± 13
The pH of the solution was 4.78. Gel strength at 24 h swelling
Means between heat and alkali gelatinization group are significantly different (p<0.05) at 20 and 25 kGy.

Table 5. Crosslinking behavior of cassava starch/PAAc super water absorbent at 15% AAc
and 75% DN
GF (%) DS (g H2O/g dry gel)
Starch (%)
15 kGy 30 kGy 45 kGy 15 kGy 30 kGy 45 kGy
0 -- -- -- -- -- --
3 -- -- -- -- -- --
5 -- -- -- -- -- --
10 51 ± 1 42 ± 3 44 ± 2 114 ± 20 305 ± 73 377 ± 64
15 61 ± 3 60 ± 1 55 ± 2 102 ± 13 144 ± 8 114 ± 20
The pH of solutions with 3%, 5%, 10% and 15% starch concentration were 5.5, 5.75, 5.46 and 6.1, respectively.
“--” no gel formation; means between varying starch (%) are significantly different (p<0.05)

Table 6. Swelling kinetics parameters of different super water absorbents

ri ks x 10-6 Theoretical DSeq Experimental DSeq
Samples R2
(g H2O/g dry gel)/min (g dry gel/ g H2O)/min (g H2O/g dry gel) (g H2O/g dry gel)
SRKC/PAAc 6.35 0.057 1667 2353 ± 170 0.9765
S/PAAc 6.43 4.880 179 182 ± 137 0.9992
Pure PAAc 6.63 0.074 1423 1374 ± 110 0.9933
Commercial 9.79 0.640 400 431 ± 34 0.9988

19
Fig 1. Scheme of Microbial Oxidative Degradation Analyzer (MODA)

20
Fig. 2. Summary of covalent reaction schemes of radiation processing of polysaccharide and
acrylic acid monomer mixture

Fig. 3. Influence of different polysaccharides on the gel properties of SWA (3%

polysaccharide, 20% AAc, 50% DN). Gel strengths were measured at swelling of 100 g/g for
CMC and 70 g/g for IC, Starch and KC. The pH of the solution with CMC, IC, Starch and KC
were 4.89, 4.92, 4.84, and 4.87, respectively.

21
Fig. 4. FTIR spectra of SWA formulations, pure polysaccharides and PAAc.

22
Fig. 5. TGA profiles of SWA formulations and their respective DTG (inset).

23
Fig. 6 Biodegradation of the radiation-synthesized super water absorbents and commercial
product

24
Fig. 7. Water retention of cassava starch/PAAc at different application rate (dry granule
application)

Fig. 8. Efficiency of water retention of cassava starch/PAAc and commercial SWAs (pre-
swollen) in soil with wet/dry cycles (S/PAAc-15 kGy-conducted in cold weather condition
while S/PAAc-20 kGy in summer)
25
Highlights

Super water absorbents (SWA) based on polysaccharides/polyacrylate were synthesized by

gamma irradiation and characterized.

Gel fraction and degree of swelling reached up to 97% and 5890 g H2O/g dry gel, respectively.

Cassava starch-based SWA biodegraded at a rate of 42% in 85 days.

CONFLICTS OF INTEREST STATEMENT

Manuscript title: Radiation-synthesized polysaccharides/polyacrylate super water absorbents and

their biodegradabilities

The authors declared no conflicts of interest.

Authors names:

Lorna S. Relleve
Charito T. Aranilla
Bin Jeremiah D. Barba
Alvin Kier R. Gallardo
Veriza Rita C. Cruz
Carlene Rome M. Ledesma
Naotsugu Nagasawa
Lucille V. Abad
 Author Statement

Manuscript title: Radiation-synthesized polysaccharide/polyacrylate super water absorbents

and their biodegradabilities

Lorna S. Relleve: Conceptualization, Methodology, Validation, Writing-Original draft

preparation, Writing-Reviewing and Editing, Visualization, Supervision, Project
Administration

Charito T. Aranilla: Conceptualization, Methodology, Visualization, Supervision

Bin Jeremiah D. Barba: Investigation, Validation, Formal Analysis, Visualization, Writing-

Reviewing and Editing,

Alvin Kier R. Gallardo: Investigation, Validation, Formal Analysis, Visualization,

Veriza Rita C. Cruz: Investigation

Carlene Rome M. Ledesma: Investigation

Naotsugu Nagasawa: Methodology, Investigation, Validation, Visualization, Supervision

Lucille V. Abad: Conceptualization, Methodology, Visualization, Supervision

Listed above are the specific contributions made by each author for this manuscript.

Lorna S. Relleve
Corresponding Author
Philippine Nuclear Research Institute – Department of Science and Technology
Commonwealth Avenue, Diliman, Quezon City, 1101, Philippines
Tel: (632) 8929-6010 to 19; Fax: (632) 8920-16-46
E-mail: lsrelleve@pnri.dost.gov.ph