Effect of Starch-Based Hydrogel On Early Growth of Corn

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Open Access Theses Theses and Dissertations
5-2018
Effect of Starch-based Hydrogel on Early Growth of Corn

Vaibhav Pathak
Purdue University
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Pathak, Vaibhav, "Effect of Starch-based Hydrogel on Early Growth of Corn" (2018). Open Access Theses.
1433.
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EFFECT OF STARCH-BASED HYDROGEL ON EARLY GROWTH OF
CORN
by
Vaibhav Pathak
A Thesis
Submitted to the Faculty of Purdue University
In Partial Fulfillment of the Requirements for the degree of
Master of Science in Agricultural and Biological Engineering
School of Agricultural & Biological Engineering

West Lafayette, Indiana
May 2018
ii
THE PURDUE UNIVERSITY GRADUATE SCHOOL

STATEMENT OF COMMITTEE APPROVAL
Dr. Rose Prabin Kingsly Ambrose, Chair

School of Agricultural and Biological Engineering
Dr. Klein Ileleji
School of Agricultural and Biological Engineering
Dr. Carl Wassgren
School of Mechanical Engineering
Approved by:
Dr. Bernard A. Engel
Head of the Graduate Program
iii
Dedicated to Maa, Papa, and Tanya

iv
ACKNOWLEDGMENTS
This project would not have been possible without the able guidance of my major professor Dr.
Kingsly Ambrose. More than anything, he has been a patient and sympathetic teacher to me. He
has been in my shoes before and understands the issues a graduate student faces. His words have
been a boost to me to work harder on my research project and to let myself grow as a researcher
in the process. For this and much more, I wish to express my most sincere gratitude to him. I also
wish to thank my committee members, Dr. Carl Wassgren and Dr. Klein Ileleji, for their valuable
feedback on the progress of the project and for offering prudent suggestions on experimental
methodologies.
During this project, I worked at several research facilities on Purdue campus. I performed most of
my preliminary growth experiments and material characterizations at the Particle Characterization
Lab and I cannot thank Dr. Dhananjay Pai enough for his constant guidance and assistance with
the use of various lab resources. I am highly grateful to Dr. Tony Zhou and Dr. Tonglei Li from
the Department of Industrial and Physical Pharmacy for permitting me to use various instruments
in their laboratories. Here, other lab members, particularly, Dr. Sharad Mangal and Nivedita Shetty
have offered their experience and time to help me with the instruments. I also wish to thank Dr.
Nathan Mosier for kindly allowing me to access the lab space, equipment and other resources of
the Laboratory of Renewable Resource Engineering (LORRE) for my chemical and physical
processing needs. Dr. Iman Beheshti, Dr. David Orrego, Raymond Redcorn and Antonio Santos
from LORRE have been very helpful and accessible for every kind of help I needed here. Finally,
I performed my final growth experiments at Purdue Horticulture’s Plant growth facility. I am
immensely thankful to Mr. Nathan Deppe, the facility manager, for sharing his insights on the
growth of corn plants which helped me design the growth experiments and later monitor the
progress of these experiments in the best possible way. I appreciate his knowledgeable advice for
my experimental needs but am equally grateful for his very amiable nature, which made working
at the facility a delightful experience.
I am fortunate to have had Camila Jange and Dr. Shankali Pradhan as my office and lab mates
during my graduate studies. They have been friends and mentors to me. I am also grateful to my
v
research group members Yanjie Chen, Yumeng Zhao, and Karthik Salish, for their willingness to
help me during my experiments.
I would be remiss if I do not acknowledge the critical support and company of some amazing
friends at Purdue. Away from my home country, my friends have been a family to me. I could not
imagine my life at Purdue without the care and love I received from them. I, therefore, wish to
extend my heartiest gratitude to Marisol Pantoja, Camila Jange, Camilo Duarte, Irma Adyatni,
Carolina Pilar, Diana Ramirez, Sonal Bhujbal, Siddharth Mehra, Sushant Mehan, Karthik Salish
and all others who I might have missed.
I am blessed by God with a lovely family. I am in eternal debt to my Maa and Papa for making me
the person that I am today. It is only their love for me that has made all my accomplishments
possible. They have made immense sacrifices and took pains to put my needs before theirs’, and
have been incredibly supportive of my professional ambitions. I cherish the presence of my dear
little sister, Tanya in my life. She can effortlessly bring a smile to my lips and fill my heart with
joy. Although she is younger to me, I have so much to learn from her. She is more precious to me
than anything. I am thankful for the powerful blessings of my grandfather and my late grandmother.
I hope I can be their joy and pride. And finally, I wish to thank God for being my source of peace,
energy, courage, love, and determination, and for acting in mysterious ways to bless me with such
good fortune.
vi
TABLE OF CONTENTS
LIST OF TABLES ......................................................................................................................... ix

LIST OF FIGURES ........................................................................................................................ x
LIST OF ABBREVIATIONS ....................................................................................................... xii
ABSTRACT ................................................................................................................................. xiii
INTRODUCTION ................................................................................................ 1
1.1 Hydrogels ............................................................................................................................ 1
1.2 Hydrogels from Natural Polymers ...................................................................................... 1
1.3 Application of Hydrogel in Agriculture .............................................................................. 2
1.4 Project overview ................................................................................................................. 3
1.5 References ........................................................................................................................... 4
LITERATURE REVIEW ..................................................................................... 6
2.1 Hydrogels and their preparation.......................................................................................... 6
2.1.1 Properties of hydrogels and their applications............................................................. 6
2.1.2 Classification of Hydrogels based on Crosslinking Bonds.......................................... 7
2.1.3 Theory of water absorption by hydrogels .................................................................... 8
2.2 Chemistry of Commercial Superabsorbent Hydrogels ....................................................... 9
2.3 Drawbacks of Synthetic Superabsorbent Hydrogels......................................................... 10
2.4 Superabsorbent Hydrogels Prepared Using Polysaccharides ........................................... 10
2.5 Polysaccharide-based Hydrogels ...................................................................................... 11
2.6 Application of Superabsorbent Hydrogel in Agriculture .................................................. 14
2.6.1 Seed Germination and Water Uptake ........................................................................ 14
2.6.2 Soil Amendment with Hydrogel ................................................................................ 15
2.6.3 Seed Treatment with Hydrogel .................................................................................. 16
2.7 References ......................................................................................................................... 17
PREPARATION AND PROPERTIES OF STARCH-BASED HYDROGEL... 23
3.1 Introduction ....................................................................................................................... 23
3.2 Materials and Methods ...................................................................................................... 23
3.2.1 Preparation of hydrogel ............................................................................................. 23
vii
3.2.2 Fourier transform-infrared spectroscopy (FT-IR) ..................................................... 24

3.2.3 Water absorption capacity ......................................................................................... 25
3.2.4 Absorption under load ............................................................................................... 26
3.2.5 Statistical analysis ...................................................................................................... 27
3.3 Results and Discussion ..................................................................................................... 28
3.3.1 Preparation of hydrogel ............................................................................................. 28
3.3.2 Fourier Transform-Infrared Spectroscopy (FT-IR) ................................................... 28
3.3.3 Water Absorption Capacity ....................................................................................... 29
3.3.4 Absorption under load ............................................................................................... 31
3.4 Conclusions ....................................................................................................................... 32
3.5 References ......................................................................................................................... 33
EFFECT OF HYDROGEL SEED COATING ON EARLY CORN GROWTH 35
4.1 Introduction ....................................................................................................................... 35
4.2 Materials and Methods ...................................................................................................... 35
4.2.1 Thin film hydrogel coating ........................................................................................ 35
4.2.1.1 In vitro germination study .................................................................................... 36
4.2.2 Hydrogel coating by seed pelleting method .............................................................. 37
4.2.2.1 Growth study in soil ............................................................................................. 39
4.2.2.2 Emergence study in soil ........................................................................................ 41
4.2.3 Statistical analysis ...................................................................................................... 42
4.3 Results and Discussion ..................................................................................................... 42
4.3.1 Thin film coating method .......................................................................................... 42
4.3.1.1 In vitro germination study .................................................................................... 43
4.3.2 Hydrogel coating by seed pelleting method .............................................................. 45
4.3.2.1 Growth study in soil ............................................................................................. 47
4.3.2.2 Emergence study in soil ........................................................................................ 53
4.4 Conclusions ....................................................................................................................... 54
4.5 References ......................................................................................................................... 55
OVERALL CONCLUSIONS AND FUTURE WORK...................................... 56
5.1 Restatement of the thesis objectives ................................................................................. 56
5.2 Conclusions on the absorption properties of the hydrogel................................................ 56
viii
5.3 Conclusions on the effect of hydrogel coating on corn plant growth ............................... 57
5.4 Future work ....................................................................................................................... 57
ix
LIST OF TABLES
Table 4.1 Composition of coating powder mixture ...................................................................... 38

x
LIST OF FIGURES
Figure 3.1 Procedure of hydrogel preparation .............................................................................. 24

Figure 3.2 Schematics of the apparatus used for measuring water absorption capacity............... 26
Figure 3.3 Schematic of the apparatus used for measuring Absorption-under-load..................... 27
Figure 3.4 FT-IR spectra of waxy corn starch and the corresponding hydrogel product. ............ 28
Figure 3.5 FT-IR spectra of potato starch and the corresponding hydrogel product .................... 29
Figure 3.6 Water absorption capacity of hydrogels in distilled water (n = 2) and 0.9% NaCl (n =
4) solution calculated using: (a) Final dry weight basis, (b) Initial dry weight basis ....... 30
Figure 3.7 Absorption under load at 4.9 kPa (0.7 psi) of hydrogels in 0.9% NaCl solution ........ 32
Figure 4.1 Counting germinated seeds during in vitro germination study ................................... 37
Figure 4.2 Corn plant growth after 14 days of planting during the growth study ........................ 40
Figure 4.3 Emergence of corn seeds during the emergence ......................................................... 41
Figure 4.4 Hydrogel loading of the four batches of thin film-coated seeds (CH1-CH4) (n = 1) . 43
Figure 4.5 Germination profile of hydrogel-coated seeds compared with uncoated seeds (n = 1)
........................................................................................................................................... 44
Figure 4.6 Time to median germination, Timson’s and Synchrony indices plotted against hydrogel
loading (n = 1)................................................................................................................... 45
Figure 4.7 Coating efficiency at different hydrogel compositions of the powder mixture (n = 20)
........................................................................................................................................... 46
Figure 4.8 Observed and expected hydrogel loading by seed pelleting method (n = 20) ............ 46
Figure 4.9 Seed corns after coating by seed pelleting method ..................................................... 47
Figure 4.10 Comparison of percent daily emergence of uncoated seeds with 1.1, 2.6 and 4.2%
hydrogel-coated seeds at 93% FC watering ...................................................................... 48
Figure 4.13 Comparison of root and shoot dry weight of uncoated seeds and hydrogel-coated seeds
on day 14 (coating levels with the same letter are not significantly different) ................. 51
xi
Figure 4.14 Comparison of root and shoot dry weight at different watering levels on day 14
(coating levels with the same letter are not significantly different).................................. 51
Figure 4.15 Comparison of root and shoot dry weight of uncoated seeds hydrogel-coated seeds on
day 21 (coating levels with the same letter are not significantly different) ...................... 52
(coating levels with the same letter are not significantly different).................................. 52
Figure 4.17 Comparison of percent daily emergence of uncoated seeds and hydrogel-coated seeds
at the two watering levels: (i) 92-93% FC, (ii) 65% FC ................................................... 53
xii
LIST OF ABBREVIATIONS
AANa Sodium acrylate

ANOVA Analysis of variance
APS Ammonium persulfate
ATR Attenuated Total Reflectance
AUL Absorption under load
CMC Carboxymethyl cellulose
CMS Carboxymethyl starch
DMAP Dimethylaminopyridine
DS Degree of substitution
DW Distilled water
EDANA International association for Nonwovens and related industries
FT-IR Fourier transform – infrared spectroscopy
HEA 2-hydroxyethyl acrylate
HEC Hydroxyethyl cellulose
INDA Association of the Nonwoven Fabrics Industry
IRE Internal reflection element
MBA N, N’-methylenebisacrylamide
NWSP Nonwovens standard procedure
PAN Polyacrylonitrile
PS Potato starch
PSH Potato starch hydrogel
RH Relative humidity
SAP Superabsorbent polymer
SPH Superporous hydrogel
WAC Water absorption capacity
WCS Waxy corn starch
WCSH Waxy corn starch hydrogel
xiii
ABSTRACT
Author: Pathak, Vaibhav. MS

Institution: Purdue University
Degree Received: May 2018
Title: Effect of Starch-based Hydrogel on Early Growth of Corn
Committee Chair: Dr. R. P. Kingsly Ambrose
Seed coating with highly absorbent polymers can potentially improve the water availability for
early growth of seeds under dry conditions and therefore prevent associated delays in the
emergence and reduced crop stand. The limited number of studies on hydrogel seed coatings have
shown that their effect on seed growth is not always beneficial, and varies with plant species,
amount of hydrogel used and amount of available water in the growing medium. The current work
studied the effect of hydrogel seed coating on the early growth of corn using starch-based
biodegradable hydrogels. The hydrogels were prepared from potato starch (PS) and waxy corn
starch (WCS) by an aqueous esterification-cum-crosslinking reaction with succinic anhydride
using dimethylaminopyridine as a catalyst, followed by neutralization of ester carboxylic acid. The
formation of the required chemical bonds in starch after the preparation procedure was verified by
Fourier transform-infrared spectroscopy. The water absorption capacity of the hydrogels was
determined in distilled water (PS: 260 g/g, WCS: 199 g/g) and 0.9% NaCl solution (PS: 18 g/g,
WCS: 38 g/g). The saline absorption capacity of the hydrogel under a load of 4.9 kPa was also
measured (PS: 7 g/g, WCS: 6 g/g). The effect of the hydrogel as a seed coating on the early growth
of corn seeds was tested in a series of experiments. In a preliminary experiment using WCS
hydrogel, the germination behavior of hydrogel film-coated corn seeds was compared under water
stress with uncoated seeds. The hydrogel-coated seeds showed an improved rate of germination.
In the following study that used PS hydrogel, the emergence and early growth of seed corn were
tested for the effect of two factors – hydrogel loading per seed (1.1, 2.6 and 4.2%) and watering
level (92-93%, 82% and 77% of field capacity or FC). A significantly higher rate of emergence
was observed in coated seed than uncoated seeds at the 77% FC watering. The rate of emergence
was significantly higher for hydrogel-coated seeds but the three coating levels were similar. This
study could therefore not determine the effect of different levels of hydrogel loading on the seeds.
At higher watering levels of 93% and 82%, the emergence of the coated seeds did not differ from
xiv
the uncoated seeds. The hydrogel coating did not have a significant effect on root and shoot dry
biomass after 14 and 21 days of sowing. In the final study using PS hydrogel, the emergence of
uncoated and hydrogel-coated seeds (4.2% level) was tested at a lower watering level (65% FC).
The hydrogel coating showed no improvement in the rate of emergence at this level of watering.
It was therefore concluded that the hydrogel coating improved the rate of seed emergence only at
moderate limitations of water in the growth medium, which might be attributed to a higher amount
of water available due to the coating. The hydrogel coating did not improve emergence at high or
very low soil water content. The hydrogel coating did not have a significant effect on the post-
emergence growth of corn plant which indicates that hydrogel coating’s contribution to plant’s
water requirements diminishes rapidly once the plant gains wider access to soil water through its
root system. In future work, a study on the kinetics of hydrogel biodegradation and the associated
loss of absorption property can give insights into its maximum functional life in the soil. The
hydrogel coating levels may be selected to have a wider range to improve the resolution of the
effect of different levels. Finally, the seed pelleting method may be checked for variability in the
deposition of the hydrogel among the seeds and, if required, the coating method improved. The
hydrogel deposition should have minimal variability among the seeds of a treatment level and
should be suitable to implement significantly different treatment levels of hydrogel loading.
1
INTRODUCTION
1.1 Hydrogels
Hydrogels or superabsorbent hydrogels are hydrophilic three-dimensional network polymers that

can absorb and retain water within their molecular matrix (Zohuriaan-Mehr & Kabiri, 2008).
Hydrogels are prepared by crosslinking or bridging hydrophilic polymer chains, either physically
or chemically, to make a flexible but non-dissolving network-like structure (Laftah, Hashim &
Ibrahim, 2011). The chemical crosslinking can be introduced by copolymerizing the monomers
with a crosslinking agent, a chemical that contains multiple functional groups for reacting.
Crosslinking a pre-formed polymer with crosslinkers is also a common preparation variation
(Sadeghi & Hosseinzadeh, 2008). Superabsorbent hydrogels find major application in diapers,
feminine hygiene, and adult incontinence products. Hydrogels, however, find application in
diverse fields like agriculture, tissue engineering, wound dressing, enzyme biosensors, contact
lenses, pharmaceutical formulations, separation devices, and catalysis (Kabiri, Omidian,
Zohuriaan-Mehr & Doroudiani, 2011).
Commercial superabsorbent hydrogels (SAPs) are commonly prepared using acrylic acid or
acrylamide monomers (Laftah et al., 2011). A free-radical polymerization reaction is used to
polymerize these monomers. A crosslinked product is obtained if the monomers are co-
polymerized with a small amount of crosslinking agent that bear two or more vinyl functional
group (Ahmed, 2015). A major drawback of these hydrogels is that they do not decompose in the
environment and are non-renewable due to their petroleum-based raw materials (Yoshimura et al.,
2006). A widespread use of these materials for disposable hygiene products has therefore created
a huge environmental burden. Moreover, the crosslinkers and monomers are usually toxic and can
persist in the final product, posing a human health hazard (Demitri, Scalera, Madaghiele, Sannino,
& Maffezzoli, 2013).
1.2 Hydrogels from Natural Polymers
To make superabsorbents eco-friendly and safer, newer materials are being developed that have a
significant part of their component derived from natural sources like polysaccharides and
2
polypeptides. Polysaccharides (starch, cellulose, agarose, carrageenan, etc.) are highly hydrophilic
molecules due to the presence of hydroxyl, or carboxyl groups on their chains. A common
approach to make hydrogels is to perform a graft polymerization of the acrylic monomers on
polysaccharides. Although polysaccharides have been used mostly as grafting substrates to
synthesize superabsorbent hydrogels (Sadeghi & Hosseinzadeh, 2008), a limited number of studies
have reported the preparation and characterization of polysaccharide-based hydrogels (Seidel et
al., 2004; Yoshimura, Yoshimura, Seki and Fujioka, 2006; Demitri et al., 2008; Demitri et al.,
2013, Wen et al., 2015). Polysaccharides can be substituted with different pendant groups, to
varying degrees, to impart desirable processing properties and reactivity (Sannino, Demitri &
Madaghiele, 2009; Ismail, Irani, & Ahmad, 2013). The native hydroxyl groups or the substituted
groups on the polysaccharide can act as sites of crosslinking reactions with multifunctional
crosslinkers via ester or ether bonds (Sannino et al., 2009; Ismail et al., 2013). A few examples of
such crosslinkers are glycerol, epichlorhydrin, carbodiimide, succinic anhydride, and dicarboxylic
acids.
1.3 Application of Hydrogel in Agriculture
Application of hydrogels in agriculture has shown much promise and is of growing interest. Most
commonly, superabsorbent hydrogels are mixed with soil to enhance the water holding capacity
of the soil. Studies have shown that hydrogel addition to soil can improve water and fertilizer
retention, improve soil aeration, reduce evapotranspiration, improve seedling emergence, and
prolong water availability for plant use (Demitri et al., 2013; Agaba et al., 2010; Guilherme et al.,
2015; Sarkar, Basak, Sarkar & Mandal, 2017).
Another use of hydrogels in crop production is application as seed coating. This technology has
already been commercialized with the promise of great benefits to seed growth. Seeds depend on
the proximity of wet soil, prolonged presence of moisture and a good soil-seed surface contact to
derive water for germination and early seedling growth. If the rate of water loss from the soil is
high, the seeds cannot germinate on time, which delays their further growth until water becomes
available. Moreover, seeds that have partially imbibed water or have germinated lose their drought-
tolerance, which makes them susceptible to death under dry conditions. Thus, dry weather
conditions during the sowing season can delay the growth or reduce the crop stand. To overcome
3
this problem, the limited water resources should be made available to the seeds in a more efficient
manner by increasing its availability and duration of contact with the seeds.
A hydrogel seed coating can localize high quantities of water near the seed and prolong its
availability. However, only a few studies have tested hydrogels as seed coating materials to
determine its effect on seed growth. Most of these studies have reported a negative influence of
seed coatings on germination (Gorim & Asch, 2012; Berdahl & Barker, 1980; Henderson, 1984).
Berdahl & Barker (1980) attributed this effect to impaired seed aeration due to excess of water
near the seed. The evaluation of hydrogel coating on barley, rye and wheat seeds by Gorim & Asch
(2012) showed that the effect on growth depends highly on species but is detrimental in all cases.
The same was concluded by Waddington (1997) who found that applying dry polyacrylamide gel
on the seeds of alfalfa and Russian wildrye had neutral to deleterious response. On the contrary,
Su, Li, Xue & Wang (2017) reported that the hydrogel coating on Caragana korshinskii improved
the germination and alleviated drought symptoms in the seeds. It can be noted that these studies
differ in the species being studied, the coating materials, the coating methods, and the design of
the growth study, which result in contradictory findings. This also makes it difficult to synthesize
the findings from these studies and extrapolate it to other hydrogels and seeds. Thus, to determine
if a new hydrogel with higher water absorption capacity can improve emergence and early growth
of corn under dry conditions, a specifically-designed growth experiment needs to be conducted.
The findings of such a study would then be applicable only to this combination of hydrogel and
plant species. This makes hydrogel seed coatings a subject that requires extensive investigation so
that their effect can be understood better and thus predicted across different plant species and
growth conditions.
1.4 Project overview
This work investigated the effect of coating seed corn with a biodegradable starch-based hydrogel
on its early growth. Through a series of studies, the role of two factors was determined viz. the
amount of water in the growth medium and the hydrogel loading on seeds. This work builds upon
the existing scientific knowledge on the behavior of hydrogel seed coatings and analyzes their
utility as an aid to plant growth under limited water availability.
4
This thesis work is divided into two parts. The first part of the study characterized the physical and
water absorption properties of the starch-based hydrogel to predict its suitability for application as
seed coating. In the second part, a series of seed growth experiments were performed to determine
the effect of various factors on the growth of hydrogel-coated seeds.
1.5 References
Agaba, H., Baguma Orikiriza, L. J., Esegu, O., Francis, J., Obua, J., Kabasa, J. D., &
Hüttermann, A. (2010). Effects of hydrogel amendment to different soils on plant
available water and survival of trees under drought conditions. Clean–Soil, Air, Water,
38(4), 328-335.
Ahmed, E. M. (2015). Hydrogel: preparation, characterization, and applications: a review.
Journal of Advanced Research, 6(2), 105–121.
Berdahl, J. D., & Barker, R. E. (1980). Germination and Emergence of Russian Wildrye Seeds
Coated with Hydrophilic Materials 1. Agronomy journal, 72(6), 1006-1008.
Demitri, C., Scalera, F., Madaghiele, M., Sannino, A., & Maffezzoli, A. (2013). Potential of
cellulose-based superabsorbent hydrogels as water reservoir in agriculture. International
Journal of Polymer Science, 2013.
Demitri, C., Del Sole, R., Scalera, F., Sannino, A., Vasapollo, G., Maffezzoli, A., Ambrosio, L.
and Nicolais, L. (2008). Novel superabsorbent cellulose‐based hydrogels crosslinked with
citric acid. Journal of Applied Polymer Science, 110(4), 2453-2460.
Gorim, L., & Asch, F. (2012). Effects of composition and share of seed coatings on the
mobilization efficiency of cereal seeds during germination. Journal of agronomy and
crop science, 198(2), 81-91.
Guilherme, M.R., Aouada, F.A., Fajardo, A.R., Martins, A.F., Paulino, A.T., Davi, M.F.,
Rubira, A.F. and Muniz, E.C. (2015). Superabsorbent hydrogels based on
polysaccharides for application in agriculture as soil conditioner and nutrient carrier: a
review. European Polymer Journal, 72, 365–385.
Henderson, J. C. (1984). Effect of hydrophilic gels on seed germination and plant establishment.
Ismail, H., Irani, M., & Ahmad, Z. (2013). Starch-based hydrogels: present status and
applications. International Journal of Polymeric Materials and Polymeric Biomaterials,
62(7), 411-420.
5
Kabiri, K., Omidian, H., Zohuriaan‐ Mehr, M. J., & Doroudiani, S. (2011). Superabsorbent
hydrogel composites and nanocomposites: a review. Polymer Composites, 32(2), 277-
289.
Laftah, W. A., Hashim, S., & Ibrahim, A. N. (2011). Polymer hydrogels: A review. Polymer-
Plastics Technology and Engineering, 50(14), 1475-1486.
Sadeghi, M., & Hosseinzadeh, H. (2008). Synthesis and superswelling behavior of
carboxymethylcellulose–poly (sodium acrylate‐ co‐ acrylamide) hydrogel. Journal of
applied polymer science, 108(2), 1142-1151.
Sannino, A., Demitri, C., & Madaghiele, M. (2009). Biodegradable cellulose-based hydrogels:
design and applications. Materials, 2(2), 353–373.
Sarkar, B., Basak, B. B., Sarkar, S., Mandal, S., & Bhaduri, D. (2017). Use of Soil Amendments
in an Integrated Framework for Adaptive Resource Management in Agriculture and
Forestry. In Adaptive Soil Management: From Theory to Practices (pp. 143-159).
Springer, Singapore.
Seidel, C., Kulicke, W. M., Heß, C., Hartmann, B., Lechner, M. D., & Lazik, W. (2004).
Synthesis and characterization of cross‐linked carboxymethyl potato starch ether gels.
Starch‐Stärke, 56(5), 157-166.
Su, L., Li, J., Xue, H., & Wang, X. (2017). Super absorbent polymer seed coatings promote seed
germination and seedling growth of Caragana korshinskii in drought. Journal of Zhejiang
University-SCIENCE B, 18(8), 696–706.
Waddington, J. (1997). Effects of including dry polyacrylamide gel with seed on establishment
of alfalfa and Russian wildrye. Canadian journal of plant science, 77(3), 381-384.
Wen, X., Bao, D., Chen, M., Zhang, A., Liu, C., & Sun, R. (2015). Preparation of CMC/HEC
crosslinked hydrogels for drug delivery. BioResources, 10(4), 8339–8351.
Yoshimura, T., Matsuo, K., & Fujioka, R. (2006). Novel biodegradable superabsorbent
hydrogels derived from cotton cellulose and succinic anhydride: Synthesis and
characterization. Journal of Applied Polymer Science, 99(6), 3251–3256.
Zohuriaan-Mehr, M. J., & Kabiri, K. (2008). Superabsorbent polymer materials: a review.
Iranian Polymer Journal, 17(6), 451.
6
LITERATURE REVIEW
2.1 Hydrogels and their preparation
Hydrogels are hydrophilic three-dimensional network polymers that can absorb and retain water,
up to 10g/g, within their molecular matrix (Kabiri, Omidian, Zohuriaan-Mehr & Doroudiani, 2011).
Superabsorbent polymers (SAPs) are a class of hydrogels that are based on acrylic monomers and
can absorb a large amount of water or an aqueous medium (up to 2000 g/g). Hydrogels are prepared
by crosslinking or bridging hydrophilic polymer chains that result in a flexible but non-dissolving
network.
2.1.1 Properties of hydrogels and their applications
Some of the most important properties of hydrogels are water absorption capacity, stimuli-
responsive swelling and deswelling, swelling rate, hydrophilicity, biocompatibility, and gel
strength (Laftah, Hashim & Ibrahim, 2011). Various hydrogels are responsive in their absorption
behavior to environmental stimuli like external medium’s pH, temperature, ionic strength,
composition, radiation, and electrical field (Zohuriaan-Mehr, Omidian, Doroudiani & Kabiri,
2010). This makes them suitable for various applications such as pH-sensitive hydrogels for
artificial muscles or actuators (Eddington & Beebe, 2004), thermo-sensitive hydrogels for
controlled drug delivery (Kang, Cheon, Khang & Song, 2006), photo-sensitive hydrogels for
artificial muscles, switches and memory devices (Suzuki & Tanaka, 1990). Due to their
biocompatibility, hydrogels are attractive materials for controlled release devices, bio-adhesive
devices and targetable therapeutic devices (Laftah et al., 2011). They can also be used in artificial
skin and for tissue engineering. The time for complete swelling of hydrogels can vary from a few
seconds to hours (Omidian, Rocca & Park, 2005). Some applications require that the hydrogels
absorb the fluid quickly such as absorption of urine or blood in hygiene products (Kabiri et al.,
2008). The rate of swelling or absorption of a polymer is dependent on particle size, porosity,
drying procedure, and structure of polymer network. Small hydrogel particles absorb faster than
large particles. While most SAPs are non-porous and depend on slower diffusion mechanism for
water absorption, a category of superabsorbent hydrogels called superporous hydrogel (SPHs) can
quickly imbibe large amounts of water by capillary forces due to their highly porous bulk and
surface structure (Omidian et al., 2005).
7
The gel strength of hydrogels determines the “real” absorption capacity i.e. the
absorption/retention of solutions under mechanical pressure (Kabiri et al., 2011). Good gel strength
is important for hydrogels for use in agriculture where hydrogel is applied in deep soil, or in
hygiene products where routine bodily movement can exert pressure on the swollen hydrogel
within the product. In agriculture, hydrogels are used for controlled release of fertilizers (Wang &
Wang, 2009; Guo, Liu, Hu, Zhan & Wu, 2005), improved fertilizer retention (Wu, Liu & Liang,
2008) and reduced consumption of water. Other applications of hydrogels include manufacturing
soft contact lenses and separation devices, performing catalysis (Kabiri et al., 2011), recycling
water in pulp and paper industry (Gupta, 2002), and recovering oil (Al-Manasir, Kjøniksen, &
Nyström, 2009).
2.1.2 Classification of Hydrogels based on Crosslinking Bonds
Hydrogels are prepared by crosslinking or bridging hydrophilic polymer chains that result in a
flexible but non-dissolving network-like structure (Laftah et al., 2011). The properties of hydrogels
are significantly affected by the nature of the crosslinking bond. There are three principal types of
bonding: covalent, ionic and hydrogen bonding (Buchholz & Graham, 1998). The covalent
crosslinks can be introduced by copolymerizing the monomers with a crosslinker molecule or by
crosslinking pre-formed polymers with di- or trifunctional molecules. The former method is
usually used for vinyl monomers and crosslinkers with multiple vinyl groups. The latter method
usually involves esterifying the pendant carboxylic groups on the polymerized monomers with
crosslinkers like glycerol or ethylene glycol with multiple hydroxyl groups. Covalent crosslinking
is permanent and stable during use. An ionically crosslinked hydrogel is formed by reacting
polyvalent ions of opposite charge with the ionic polymer chains. The association of unlike charges
is very fast and therefore crosslinking is difficult to control. The structure is susceptible to drastic
changes in the presence of foreign ions that can exchange with the existing crosslinker ions. Finally,
a physical crosslink is usually formed by hydrogen bonding between segments of different polymer
chains. These crosslinks can be easily destroyed by heating the hydrogel. Usually, a physical
crosslink involves large segments of chains and hence the mass efficiency of crosslinking is poor
(Ross-Murphy, 1991)
8
2.1.3 Theory of water absorption by hydrogels
The absorption behavior of a polyelectrolyte hydrogel can be attributed to its four properties
(Sannino, Maffezzoli & Nicolais, 2003): (1) highly hydrophilic molecules or chains which
promote solvation in the presence of aqueous solution, (2) polyelectrolyte hydrogels have free
counter-ions associated with the fixed ionic charges on the chains which increase the osmotic
potential of hydrogel, (3) the fixed ionic charges on the chains which cause the hydrogel to show
Donnan-type electrochemical equilibrium when in contact with aqueous solution. At equilibrium,
the hydrogel is partially depopulated of the free counter-ions that cause repulsion between the
fixed ions and thus expansion of the network, and (4) the crosslinked network of the hydrogel
which exerts an elastic or contractile response to swelling and counteracts it by increasing the
pressure potential of water in the hydrogel. The three former properties cause the hydrogel to
absorb solutions while the fourth property limits it. These properties of the hydrogel are known to
be dependent on the chemical/structural nature of the polymer chains, the concentration of ionic
groups, the degree of polymer crosslinking, and their molecular weights. Polymers chains with
high molecular weights are more suitable for hydrogel preparation (Buchholz & Graham, 1998).
As the degree of crosslinking increases, the hydrogel’s absorption capacity initially increases due
to effective formation of a three-dimensional network. However, at higher crosslinking, the
hydrogel network becomes inflexible to expansion and the absorption capacity is reduced (Laftah
et al., 2011).
The absorption phenomenon of a hydrogel is highly dependent on the environment in contact with
the hydrogel. If the external solution has dissolved ions, the osmotic potential difference between
the hydrogel and the external solution is reduced and the repulsion between the fixed ionic charges
is partially “screened” by the internalization of the external ions with opposite charge. This reduces
the driving force for absorption which is overcome by the elastic force of the network and the
hydrogel swells to a lower degree. If an external mechanical pressure is applied to the hydrogel
during absorption, the hydrogel swelling is again reduced.
9
2.2 Chemistry of Commercial Superabsorbent Hydrogels
Hydrogels have been prepared from a variety of hydrophilic materials: natural or synthetic;
monomeric or polymeric and can be a homopolymer or a copolymer (Laftah et al., 2011).
Commercial superabsorbent hydrogels (SAPs) are commonly prepared using acrylic acid and
acrylamide (Laftah et al., 2011). A free-radical polymerization reaction is commonly used to
convert these monomers to respective polymers and their crosslinked structures (Ahmed, 2015).
The monomers can be polymerized in their acid form or their partially neutralized form, which can
lead to different polymer properties owing to the reaction occurring among uncharged or ionic
monomers, respectively (Buchholz & Graham, 1998). An initiator molecule produces free-radicals
in the reaction mixture to initiate the polymerization. Thermally decomposable initiators,
photochemical initiators, redox systems or their combinations can be used. A crosslinker can
bridge acrylic polymers via their two or more vinyl groups that can become incorporated in
different neighboring growing polymer chains. Thus, crosslinkers are usually added to the
monomers before initiation and then copolymerized. They range from di-functional compounds,
such as ethyleneglycol dimethacrylate, to tri-functional compounds, such as triallylamine, and
tetra-functional compounds, such as tetraallyloxyethane. Unintended intra-molecular bridging or
cyclization is a common phenomenon with crosslinkers (Buchholz & Graham, 1998). Crosslinkers
can modify the swelling and mechanical properties of the SAP, and affect the soluble and gel
fractions of the reacted polymer (Buchholz & Graham, 1998). The cross-linking efficiency is
affected by the steric crowding of the crosslinking arms of the crosslinker during the reaction, the
tendency of the crosslinker to form intramolecular addition reactions and the solubility of the
crosslinker in the monomer solution (Buchholz & Graham, 1998).
The acrylic acid polymerization is usually performed in an aqueous medium with two processing
variations: bulk solution polymerization, in which an aqueous solution of monomers, initiators,
and crosslinkers undergoes reaction as a whole; suspension polymerization in which the aqueous
solution is dispersed as small droplets in a hydrocarbon before the reaction is initiated in the
aqueous phase. Suspension polymerization is used for the smaller scale of production relative to
bulk solution polymerization. The dominant commercial superabsorbent technology involves
solution polymerization of acrylic acid without a graft substrate (Buchholz & Graham, 1998).
10
2.3 Drawbacks of Synthetic Superabsorbent Hydrogels
Major drawbacks of commercial superabsorbent polymers are that they are non-biodegradable and
are based on non-renewable raw materials. In addition, these products contain low levels of toxic
monomer residues that can harm the ecosystems (Demitri, Scalera, Madaghiele, Sannino, &
Maffezzoli, 2013). Since a major application of these polymers is in the disposable consumer
products, such as diapers, feminine hygiene, and adult incontinence, these polymers create a huge
non-degrading environmental burden and pollution (Yoshimura, Matsuo & Fujioka, 2006a).
Numerous scientific literature has been published that introduce new superabsorbent materials that
are partly or wholly based on natural or biodegradable materials. Commercial manufacturers are
also introducing superabsorbent products with the improved environmental profile. BASF’s
“HySorb® biomass balanced” introduces renewable feedstock like biogas and bio-naphtha into an
otherwise completely petroleum-based production process (“HySorb® biomass balanced”,
Retrieved from https://personal-care-hygiene.basf.com/en/Hygiene/HySorb-biomass-
balanced.html). This product has also been certified to enhance the sustainability of superabsorbent
products and reduce greenhouse emissions.
2.4 Superabsorbent Hydrogels Prepared Using Polysaccharides
In 1970’s, a novel superabsorbent was developed at the Northern Regional Research Laboratory
of the U.S. Department of Agriculture as an alternative to the wholly synthetic superabsorbent
products (Weaver, Bagley, Fanta & Doane, 1976). This polymer was prepared by graft-
polymerizing acrylonitrile to starch and hydrolyzing the pendant nitrile groups to carboxyl or
carboxamide groups. The crosslinking is based on hydrogen bonding within the partially swollen
starch granules. Although the raw materials are inexpensive, the preparation requires many
processing steps and great care in handling the toxic acrylonitrile monomer. The product also
suffers from a relatively large amount of soluble fraction compared to covalently crosslinked
polymers (Buchholz & Graham, 1998). The technology progressed to involve using acrylic acid
monomer for graft polymerization on starch, which became the first commercial method to
produce superabsorbent polymers (Masuda, Nishida & Nakamura, 1978). More recently, Parvathy
and Jyothi (2012) prepared and characterized a similar superabsorbent material from cassava
11
starch. It was prepared by a free radical graft copolymerization of acrylonitrile monomer on

cassava starch, before alkali hydrolysis. With a starch composition of 33%, this polymer showed
a water absorption capacity of 425 g/g after soaking in water for 2 h.
Similar superabsorbent materials have been prepared recently that have a significant part of their
component derived from natural sources. These efforts have led to superabsorbents with higher
biodegradability. Sadeghi & Hosseinzadeh (2008a,b) prepared and optimized the absorption
capacity of graft copolymers of polyacrylonitrile with starch and carboxymethyl cellulose (CMC)
as the natural component. The preparation method involved alkaline hydrolysis of a physical
mixture of the natural polymer and poly(acrylonitrile) (PAN). This causes grafting of PAN on the
polysaccharide, crosslinking among the PAN chains, and conversion of acrylonitrile groups on
PAN chains to a mixture of carboxylate and carboxamide groups. With a PAN/polysaccharide
ratio of 1.5, the highest absorption capacity of >500 g/g was obtained for both the products after
soaking in water for 3 h. The synthesis is simple and does not use toxic monomers. Also, since it
does not involve a free-radical reaction, the preparation can be carried out without nitrogen purging
of the mixture to remove oxygen. With a remarkable polysaccharide composition of ~33%, the
product is a huge improvement over completely synthetic superabsorbents.
Pourjavadi, Samadi & Ghasemzadeh (2008) prepared a fast-swelling starch-graft polymer with a
mixture of two synthetic monomers: 2-hydroxyethyl acrylate (HEA) and sodium acrylate (AANa).
The free radical copolymerization used ammonium persulfate (APS) as initiator and N, N’-
methylenebisacrylamide (MBA) as cross-linker. At a starch composition of 33% and HEA:AANa
= 0.5, the polymer showed highest water absorption capacity (180 g/g) and highest absorption-
under-load (29.3 g/g).
2.5 Polysaccharide-based Hydrogels
Although polysaccharides (starch, cellulose, agarose, carrageenan, etc.) have been introduced
mostly as grafting substrates to synthesize superabsorbent hydrogels (Yoshimura et al., 2006a;
Fujioka, Tanaka, & Yoshimura, 2013; Guilherme et al., 2015), a limited number of studies have
also focused on purely polysaccharide-based hydrogels. Polysaccharides have highly hydrophilic
molecules due to the presence of numerous polar hydroxyl groups on their repeating monomer
12
unit. These groups of polysaccharides can be substituted with different pendant groups, to varying
degrees, to impart desirable processing properties (Wesslén & Wesslén, 2002). These hydroxyl
groups or their substituted groups can act as anchors for crosslinking reactions via polyfunctional
crosslinkers that bear complementary groups for making an ester or ether bond (Sannino, Demitri
& Madaghiele, 2009; Ismail, Irani & Ahmad, 2013). A few examples of such crosslinkers are
glycerol, epichlorhydrin, carbodiimide, and dicarboxylic acids.
Sodium carboxymethyl cellulose (CMC) has been used to make the superabsorbent material. It is
a semisynthetic ionic polysaccharide that produced superabsorbent materials upon crosslinking.
This material has several disadvantages: CMC is moderately expensive; it has a low molecular
weight that limits its utility as a superabsorbent; and the crosslinking reactions are inefficient due
to existing carboxymethyl substitution (Buchholz & Graham, 1998). Demitri et al. (2008) reported
a novel SAH based on a mixture of carboxymethyl cellulose (CMC) and hydroxyethyl cellulose
(HEC) that was crosslinked by citric acid. In a later study by Demitri et al. (2013), the HEC/CMC
mixture was crosslinked by 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide with citric acid as
catalyst. This hydrogel showed a maximum swelling ratio of about 75 in distilled water and a
positive effect on soil’s water retention and sustained water release to plants. A pH-sensitive
hydrogel was prepared by Wen et al. (2015) by crosslinking a mixture of HEC and CMC with
methylenebisacrylamide using ammonium persulfate as initiator. The swelling degree was found
to be highest at pH 5 (110 g/g); it decreased drastically under acidic pH and fell gradually with
increasing alkalinity.
Alginate is another ionic polysaccharide that is derived from sea weed like giant kelps. It is
composed of D-mannuronic acid and L-guluronic acid monomers that have carboxylic acid
pendant groups. It can also be crosslinked to produce superabsorbent material but is commercially
unsuitable due to its high raw material price (Buchholz & Graham, 1998).
Yoshimura et al. (2006a) prepared a superabsorbent polymer from cotton cellulose by an

esterification-cum-crosslinking reaction with succinic anhydride in the presence of
dimethylaminopyridine (DMAP). In another study by Yoshimura, Yoshimura, Seki & Fujioka
(2006b), potato starch was modified using similar procedure and was found to show
13
superabsorbent properties. The crosslinking was attributed to both, partial diester formation and
physical interaction of carboxylate ions with charged DMAP. The cellulose and starch-based
superabsorbents had an absorption capacity of 400 and 120 g/g respectively in distilled water. The
swelling of cellulose-based SAP in 0.9% NaCl solution (100 g/g) was found to be higher than that
of sodium polyacrylate hydrogels (60 g/g). The products were found to be completely
biodegradable. In separate studies, Yoshimura, Uchikoshi, Yoshimura & Fujioka (2005) and
Fujioka et al., (2013), applied the esterification process to chitin and guar gum that resulted in
similar superabsorbent products.
Radiation crosslinking of the polymer chain to prepare hydrogels has gained attention as it does
not require crosslinker molecules and other reagents and precludes washing of the product of
unreacted substances. Fei, Wach, Mitomo, Yoshii & Kume (2000) studied hydrogel preparation
from CMC using gamma irradiation. The effect of CMC concentration and degree of
carboxymethyl substitution (DS) on gel formation was studied and it was found that higher
concentration and higher DS favored crosslinking and gel formation. The swelling ratio decreases
with increasing dose of radiation due to increasing crosslinking density. The maximum swelling
ratios of 165 and 78 were shown in water and in 0.9% NaCl solution, respectively. Nagasawa,
Yagi, Kume & Yoshii (2004) performed an identical study with carboxymethyl starch (CMS) and
found similar results. The absorption capacity of radiation-crosslinked CMS in water was higher
than that of radiation-crosslinked CMC (500 vs. 165 g/g). The absorption in 0.9% NaCl was about
25 g/g of the CMS-based hydrogel.
Seidel et al. (2001) prepared carboxymethyl starch (CMS) based hydrogels using different
polyfunctional carboxylic acids as a crosslinker and studied their rheological properties for food
and medical applications. Seidel et al. (2004) prepared and characterized another potato CMS-
based hydrogel crosslinked by dichloroacetic acid. This hydrogel was studied for its rheological
suitability as an ultrasonic gel. Its highest free swelling ratio was found to be 77.
14
2.6 Application of Superabsorbent Hydrogel in Agriculture
2.6.1 Seed Germination and Water Uptake
Imbibition of water is essential for successful seed germination. The movement of water from the
soil in the immediate vicinity to the seed is driven by a difference in the water potential of the seed
and the soil (Bewley, Bradford, Hilhorst, & Nonogaki, 2013). The water uptake occurs until the
water potential of soil and seed equalize. The completion of germination is contingent upon the
amount of water imbibed by the seed. Another crucial factor affecting water uptake is the ease of
movement of water through the soil to the seed i.e. the soil hydraulic conductivity. As soil becomes
drier, hydraulic conductivity decreases exponentially (Bewley et al., 2013).
The phenomenon of water uptake by seeds can be divided into three phases (Bewley et al., 2013).
In Phase I, the seed rapidly absorbs water owing to its very low water potential. The water enters
through the cracks in the seed coat and begins to hydrate the tissue and solutes. This phase
witnesses the beginning of respiration and other regulatory processes that require oxygen. The
water uptake continues until the turgor pressure developed in the seed cells counteract the potential
gradient. The imbibition slows down to an approximately constant water content as the seed enters
Phase II. In the second phase, also called a pause or transition phase, there is no change in the seed
water content, respiration rate or seed morphology. However, several metabolic processes get
activated depending on the hydration level of the seed. If the seed is sufficiently hydrated, the seed
will complete germination (radical emergence) and enter Phase III. The water uptake in Phase III
increases as the cells expand and cause protrusion of the radical. The driving force for water uptake
in Phase III is the enrichment of cells with osmotically active substances and the relaxation of their
cell walls, making the osmotic and pressure components of seed water potential favorable.
The duration of each of the phases of water uptake depends on temperature and soil water potential
(Bewley et al., 2013). The effect on Phase I is relatively low as water imbibition is driven by a
large water potential gradient. However, a reduction in temperature or soil water potential can
significantly affect Phase II, and the attainment of Phase III. The final water content attained in
Phase II depends on the soil water potential and if a certain minimum amount of water content is
not reached, Phase II is indefinitely extended. The minimum water content signifies water for
15
embryo expansion leading to germination. This is apparently caused by a threshold soil water
potential below which the seeds cannot absorb water.
2.6.2 Soil Amendment with Hydrogel
Seeds need a prolonged presence of moisture in their proximity for imbibition. They can be easily
hindered if the soil has low water potential and subsequently low hydraulic conductivity to replace
the water near the seed. Thus, seeds fail to complete germination on time if the water in the soil is
lost to evaporation or percolation very quickly. Mixing a superabsorbent polymer with soil is a
commonly used technique to improve soil water retention and plant water availability. Numerous
studies have shown that hydrogel amendment of soil has a positive effect on plant/tree survival,
seed emergence and/or biomass yield. Mangold & Sheley (2007) found that mixing an acrylamide
copolymer hydrogel to soil improved the emergence, biomass yield, and survival of wheatgrass
seedlings. In a study by Dorraji, Golchin & Ahmadi (2010) on the growth of corn under well-
watered conditions, loamy sand soil responded better than sandy clay loam to use of a hydrophilic
polymer as shown by soil water holding capacity, plant biomass yield, and water use efficiency.
Another set of studies investigated the effect of five different soil types and two levels of hydrogel
addition to soil on the growth of nine tropical and temperate tree species. These two studies, Agaba
et al. (2010) and Orikiriza et al. (2009), used water stress and non-water stress conditions,
respectively. Under water stress, the plant available water content of the soil increased due to
hydrogel amendment but the increase was higher in sand than loamy and clay soils. Hydrogel
addition was characterized by a decreased rate of evapotranspiration and thus the water loss
associated with it. The tree survival time also increased in most of the tree species and soils and
this was correlated positively with the increase in plant available water of the soil. In the second
study with non-water stress conditions, the root weight was higher for eight of the nine tree species
while the stem, leaf and twigs dry weight were higher for all the species grown with hydrogel. This
indicated that hydrogel addition enhances the efficiency of water uptake and photosynthesis of
these trees even when they are grown on well-watered soil. Johnson & Piper (1997) showed that
higher tomato shoot dry weights and marketable fruit yields could be obtained in soils treated with
crosslinked water-storing polymers (polyacrylamide and a starch copolymer) than untreated soils
under intermittent moisture stress conditions. The authors concluded that this was caused by higher
water use efficiency and/or higher nutrient uptake efficiency.
16
2.6.3 Seed Treatment with Hydrogel
Hydrogel seed coating has been proposed and studied as a technique to increase water availability
to seeds during germination and early growth. The hydrogel can absorb a high amount of water
and localize it near the seed. This water can be released gradually and made available to the seeds
for a longer duration. The hydrogel can also retain soluble fertilizer in the water and release it
slowly over time. This can prevent washing away of these fertilizers and increase the efficiency of
their utilization for plant nutrition.
Berdahl & Barker (1980) tested the effectiveness of seed coating on Russian wild rye seeds with
five types of hydrophilic materials by growing them under various levels of suboptimal soil water
potentials. None of the coated seeds had higher emergence or higher rate of emergence relative to
the uncoated seeds. A higher concentration of hydrophilic materials in the seed coating increased
the water uptake, but this also hindered aeration of the seeds which caused reduced germination.
Henderson (1984) tested two absorbent materials for seed coating of beans, tomato, peas, okra,
and several deciduous hardwoods and pines. Using 1% and 2% hydrogel loading by seed weight
and using three levels of irrigation regimes, the effect of hydrogel on the rate of emergence,
seedling height and total dry biomass was determined. None of these indicators of growth were
significantly affected by hydrogel coating for these species and by the moisture level.
Gorim & Asch (2012) studied the effect of hydro-absorber seed coating on the germination rates,
resource partitioning and mobilization efficiency of barley, rye and wheat seeds. The study tested
different coatings at different ratio of the total seed mass. The water supply was not limited for
this study. Germination rates for coated seeds were significantly lower than uncoated seeds. A
higher ratio of hydro-absorber coating had higher germination rates. The germination rates in
coatings with the highest ratio were similar to the uncoated control seeds and it was lower for
coatings with a smaller ratio.
In another study by Gorim & Asch (2017), two commercial hydro-absorbers – Stockosorb® and
Geohumus® seed coatings were tested for drought mitigation in two sorghum varieties. The
growth was assessed using biomass, root length, plant height, leaf area, and extension rate. Both
17
hydro-absorbers had a negative effect on growth under well-watered conditions while there was
no improvement under reduced watering. The study highlighted that the effect of hydro-absorbers
on sorghum growth was dependent on the nature of the hydro-absorber and the watering conditions.
The study, therefore, recommends that the combination of seed coat constituents and seed variety
needs extensive testing to determine suitable matches for desired growth performance.
Su et al. (2017) however found that coating the seeds of Caragana korshinskii with different
superabsorbent polymers improved germination percentage and germination energy under
drought-like conditions. Also, the coated seeds showed reduced values of several indicators of
drought stress during germination like relative electrical conductivity, proline content,
malondialdehyde, H2O2 content, and peroxidase activity.
It can be noted that the studies on hydrogel coatings differ in the species being studied, the coating
materials, the coating methods, and the design of the growth study. This might have contributed
to the differences in the observed behavior of hydrogel coating. This also makes it difficult to
synthesize the findings from these studies and extrapolate it to other hydrogels and seeds. Thus, to
determine if a new hydrogel with good water absorption capacity can improve early growth of a
plant under dry conditions, a specifically-designed growth experiment needs to be conducted. The
findings of such a study would then be applicable only to this combination of hydrogel and plant
species. This makes hydrogel seed coatings a subject that requires extensive investigation so that
their effect can be understood better and thus predicted across different plant species and growth
conditions.
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21
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22
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23
PREPARATION AND PROPERTIES OF STARCH-

BASED HYDROGEL
3.1 Introduction
This chapter describes the preparation of biodegradable hydrogels and determined their properties
which are important for their application in agriculture for the conservation of soil water. The
hydrogels were prepared from potato starch and waxy corn starch using a method adopted from
Yoshimura, Yoshimura, Seki, and Fujioka (2006a). This method involves esterification of starch
with succinic anhydride in an aqueous medium with dimethylaminopyridine as a catalyst. This
hydrogel has been reported to have high water absorption capacity and high biodegradability
(Yoshimura et al., 2006a). The current thesis work determined properties of this hydrogel that are
important for its application in agriculture.
3.2 Materials and Methods
3.2.1 Preparation of hydrogel
The hydrogel preparation method was based on the method of Yoshimura et al. (2006a) with
several modifications (Figure 3.1). The hydrogel was prepared using two starches: potato starch
(PS) and waxy corn starch (WCS). The process involved the reaction of starch and succinic
anhydride in an aqueous medium catalyzed by dimethylaminopyridine (DMAP). Starch (1 g) was
uniformly dispersed in distilled water (99 g) and gelatinized by heating the suspension at 95°C for
10 min to obtain a 1% (w/w) gelatinized starch solution. The solution was cooled to room
temperature using an ice-cold water bath. After cooling, 2.38 g of DMAP was added to the solution
and stirred until complete dissolution. To the obtained mixture, 37.2 g of succinic anhydride
powder (molar ratio of the hydroxyl group of starch: 20) was added and the esterification reaction
was allowed to occur for 24 h at room temperature. After 24 h, the reaction mixture was neutralized
by adding 148 g of 10% (w/w) aqueous solution of sodium hydroxide. In order to extract the
hydrogel, the alkalized mixture was poured into 500 ml of methanol and mixed for a few minutes.
This caused the hydrogel to precipitate as a white gel. The supernatant was decanted off and the
precipitate was air-dried in a fume hood for 3-4 h to remove traces of methanol. The solids were
then dried in a convection oven at 40 °C for 24 h. The dried solids were milled using a cutting mill
24
(Mini-Mill, Thomas® Scientific, Swedesboro, NJ) to < 1 mm particle size. Thus, the hydrogels
based on potato starch (PSH) and waxy corn starch (WCSH) were obtained in powder form. The
hydrogel yield of PSH was determined based the theoretical and observed number of moles of
esterified anhydroglucose residues with DS = 0.3 (Yoshimura et al., 2006a) produced from 1 g of
starch. Yield is defined as:
𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠

𝑌𝑖𝑒𝑙𝑑 = 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 ∗ 100 (3.1)
Figure 3.1 Procedure of hydrogel preparation
3.2.2 Fourier transform-infrared spectroscopy (FT-IR)
The FT-IR spectrum of a chemical compound gives information about different types of chemical
bonds constituting the compound. The chemical bonds in a compound absorb radiation at certain
wavelengths and could be detected by a change in the intensity of radiation at these wavelengths
when the radiation passes through a sample of this compound. The FT-IR spectra of the hydrogels
were obtained to verify the formation of essential chemical bonds. The FT-IR spectra of starch and
the corresponding hydrogel were obtained using the Cary 670 FTIR Spectrometer (Agilent
Technologies, Santa Clara, CA) with Attenuated Total Reflectance (ATR) accessory. The powder
samples were spread over internal reflection element (IRE) of the ATR for measurement and the
background was taken without any material on the element. The spectra of the starch and the
25
hydrogel were measured in the range of 600 to 4000 cm-1 with a resolution of 4 cm-1. For each
sample, three replicates were obtained and each measurement involved an instrumental averaging
over 32 sample scans. If the spectral peaks did not show variation across the replicates, the
measurement with the highest intensity was selected. The background was measured before each
sample measurement as an instrumental average of 32 scans.
3.2.3 Water absorption capacity
The water absorption capacity (WAC) is the equilibrium amount of water that can be absorbed by
a given amount of hydrogel when in contact with an excess of aqueous solution without an
additional mechanical load applied on the hydrogel. WAC of a hydrogel reduces as the ionic
strength of the external media being absorbed increases (Kazanskii & Dubrovskii, 1992). This loss
in absorption capacity is usually determined by measuring WAC at 0.9% (w/w) NaCl (Mao, 2016).
This concentration is corresponding to that of physiological saline and is commonly used owing
to a major application of superabsorbent hydrogels in absorbing bodily fluids like urine and
menstrual fluid (Kabiri, Omidian, Zohuriaan-Mehr & Doroudiani, 2011). WAC of the two
hydrogels was thus determined in two aqueous media: distilled water and 0.9% aqueous NaCl
solution (physiological saline).
The method used in this study was similar to the “tea bag” method (Zohuriaan-Mehr & Kabiri,
2008) with some minor modifications (Figure 3.2). About 0.2 g of dry hydrogel powder was
weighed (initial dry weight) and placed at the bottom of a 5-micron filter paper cone and the cone
was lowered into a 200-ml beaker containing 150 ml of distilled water. It was ensured that the
hydrogel was submerged, and the cusp of the cone was above the solution level in the beaker.
Thereafter, some water was added to the cone to fill it to the brim. The hydrogel was allowed to
absorb water for 48 h to reach equilibrium absorption. After 48 h, the cone was removed from the
beaker and excess water drained under gravity for 10 minutes. Then, the cone containing the
swollen hydrogel was carefully unfolded and placed flat on a paper towel to wick away excess
surface water. The swollen hydrogel was collected and weighed. The dry weight of the swollen
gel was obtained after drying it at 30 ˚C for 48 h (final dry weight). The water absorption capacity
was calculated as the ratio of the weight of absorbed water to the weight of the dry hydrogel. The
WAC was calculated using two values of hydrogel dry weight – initial dry weight and final dry
26
weight. These two weights were different due to the dissolution of a portion of the hydrogel
product and loss of material along with the filter paper during the WAC test. It is to be noted that
final dry weight may correspond more closely to the insoluble or gel fraction of the hydrogel while
the initial dry weight corresponds to a mixture of soluble and gel fractions of the hydrogel product.
Thus, the WAC obtained using the two dry weight values could be interpreted accordingly. The
WAC was reported as an average value of two replicates for distilled water and four replicates for
saline solution. The following equation was used to calculate WAC:
weight of swollen hydrogel−weight of dry hydrogel

WAC = (3.2)
weight of dry hydrogel
Figure 3.2 Schematics of the apparatus used for measuring water absorption capacity
3.2.4 Absorption under load
The absorption under load (AUL) is a commonly used property of a superabsorbent hydrogel to
characterize its capacity to absorb a solution under pressure. The method used in this study is based
on the Nonwovens standard procedure (NWSP) 242.0.R2(15) published by the international
association for the nonwovens and related industries (EDANA) and Association of the Nonwoven
Fabrics Industry (INDA) with minor modifications. A schematic diagram of the AUL apparatus is
shown in Figure 3.3. The hydrogel (~ 0.15 g) was spread uniformly on a filter paper over a circular
area of diameter 3.7 cm and enclosed by a hollow cylindrical shell of identical internal diameter.
After placing the shell around the test sample, a cylindrical piston load (diameter 3.7 cm) was
27
slowly inserted into the shell and gently placed on the sample. The load was selected to apply a
uniform pressure of 50 g/cm2 or 4.9 kPa on the sample. This assembly was then placed on a
combined stack of filter papers (2), paper towels (24 layers) and flat sponges that conducted 0.9%
w/w NaCl solution from a petri dish by capillary action. The yielding of the stack under load was
prevented by placing supports in between the sponges. The flat hydrogel sample was thus put in
indirect contact with the solution while under load. The hydrogel was allowed to absorb water for
1 h and then the cylindrical shell, the piston load, and the filter paper holding the test sample were
simultaneously lifted off the wet paper towels. The swollen hydrogel was carefully collected,
weighed and then dried in a convection oven at 40 °C for 24 h to obtain the final dry weight. In
order to account for the loss of hydrogel material during the test, either due to dissolution or the
residue on the apparatus, the reported values of AUL are based on final dry weight instead of the
initial dry weight. The AUL results have been reported as the average of two replicates. The AUL
was calculated using the following relation:
weight of swollen hydrogel under load−weight of dry hydrogel

AUL = (3.3)
weight of dry hydrogel
Figure 3.3 Schematic of the apparatus used for measuring Absorption-under-load
3.2.5 Statistical analysis
The water absorption capacity of PSH and WCSH were compared in both types of solutions using
1-way ANOVA. The absorption under load of the two hydrogels was compared similarly.
28
3.3 Results and Discussion
3.3.1 Preparation of hydrogel
The preparation of hydrogel was performed in water as hot water is a good solvent for starch.
Water is also a safe, environment-friendly and cheaper solvent. However, the esterification
reaction is highly reversible in water which leads to a low degree of substitution (DS) of succinic
anhydride on starch (Yoshimura et al., 2006a). The molar ratio of succinic anhydride to the
hydroxyl group on starch that was used for this reaction was 20 to get a product with higher DS
and therefore a high absorption capacity. The hydrogel product was insoluble in methanol and
precipitated quickly with an excess of methanol. The insolubility of hydrogel in methanol may be
a result of low DS. The reaction yield for PSH was 41 ± 2 % (n = 2).
3.3.2 Fourier Transform-Infrared Spectroscopy (FT-IR)
The IR spectra of the hydrogels and their corresponding unmodified starches were obtained as
shown in Figure 3.4 and 3.5.
1550 cm-1 1735 cm-1

Waxy corn starch
Transmittance
Waxy corn starch hydrogel
0 500 1000 1500 2000 2500 3000 3500 4000 4500

-1
Wavenumber (cm )
Figure 3.4 FT-IR spectra of waxy corn starch and the corresponding hydrogel product.
29
1550 cm-1 1735 cm-1

Potato starch
Transmittance
Potato starch hydrogel
0 500 1000 1500 2000 2500 3000 3500 4000 4500

Wavenumber (cm-1)
Figure 3.5 FT-IR spectra of potato starch and the corresponding hydrogel product
For both hydrogels, two new transmittance peaks appear at 1735 and 1550 cm-1 which correspond
to the stretching of a carboxyl group (C=O) of the ester bond and carboxylate ion (-COO−)
respectively (Yoshimura, Matsuo & Fujioka, 2006b). These wavenumbers are highlighted in the
figure using vertical lines, showing that these peaks are not present in the spectrum of unmodified
starches. This verifies the formation of an ester bond between the hydroxyl group of starch and
succinic anhydride, as well as the formation of carboxylate ion due to alkalization.
3.3.3 Water Absorption Capacity
The average water absorption capacity of the two hydrogels in distilled water (DW) and 0.9%
NaCl (saline) are summarized in Figure 3.6.
It was observed that the presence of 0.9% NaCl salt in the aqueous external media reduced the
absorption capacity of both hydrogels compared to that of absorption in distilled water. This
phenomenon may be explained by the mechanism of absorption (discussed in section 2.1.3) in
30
superabsorbent hydrogels which contain fixed ionic groups on their molecular chains as well as
free ions associated with these group (Sannino, Maffezzoli, & Nicolais, 2003). The starch-based
hydrogel contains fixed carboxylate ions associated with free sodium ions. The osmotic pressure
due to free ions and the network expansion due to repulsion between the fixed ionic groups is
responsible for absorption of water by the hydrogel. In the presence of salt or ions in the external
solution, which is NaCl for this absorption test, the osmotic potential difference between the
internal and the external of the hydrogel is reduced and the repulsion force between the carboxylate
ions is weakened due to limited outward diffusion of the free sodium ions. Therefore, a lower
amount of solution is absorbed.
Distilled water 0.9% NaCl Distilled water 0.9% NaCl

300 300
Water absorption capacity (g/g)

Water absorption capacity (g/g)
250 250
200 200
150 150
100 100
50 50
0 0
Potato starch Waxy corn starch Potato starch Waxy corn starch
a) Final dry weight basis b) Initial dry weight basis

Figure 3.6 Water absorption capacity of hydrogels in distilled water (n = 2) and 0.9% NaCl (n =
4) solution calculated using: (a) Final dry weight basis, (b) Initial dry weight basis
The higher absorption capacity of potato starch-based hydrogel compared to waxy corn starch-
based hydrogel in distilled water may be explained by the presence of a higher phosphate ester
substitution in native potato starch. The negatively-charged phosphate groups repel each other and
therefore increase the interaction of starch with water by reducing the intermolecular association
via hydrogen bonding. This characteristic of potato starch causes its higher swelling power and
solubility in water after gelatinization (Swinkels, 1985). For the potato starch hydrogel, the ionic
carboxylate groups will be supplemented by the phosphate groups. The higher ionic content in the
31
hydrogel is likely to attract more water and lead to a higher water absorption capacity. The water
absorption capacity of the two types of hydrogels in saline solution was found to be similar
(ANOVA, ɑ = 5%).
The absorption capacity of the starch-based hydrogels was found to be lower than that reported for
superabsorbent hydrogels prepared by graft copolymerization of starch with acrylic monomers like
acrylic acid (1077 g/g in DW and 61 g/g in saline; Li, Zhang & Wang, 2007) and acrylamide (425
g/g in DW; Parvathy & Jyothi, 2012).
3.3.4 Absorption under load
The AUL for the two types of hydrogels is shown in Figure 3.7. Based on one-way ANOVA (ɑ =
5%), the two hydrogels were not significantly different in their AUL values. The AUL in 0.9%
NaCl solution for both the hydrogels was drastically lower than the unloaded absorption capacity
in 0.9% NaCl solution and significantly lower than the absorption in distilled water. This
phenomenon may be explained by the increased hydrostatic pressure inside the gel network due to
the load which along with the contractile force of the molecular network counters the forces driving
the absorption. The ability of a hydrogel to resist desorption under load is measured by its elastic
modulus (Buchholz & Graham, 1998). The elastic modulus of a hydrogel increases with its
crosslinking density. The crosslinking density in the starch-based hydrogel can be correlated to the
degree of substitution (DS) of starch by succinic anhydride, which was found to be very low for
the hydrogel prepared by Yoshimura et al., 2006a. Therefore, a low crosslinking density may
explain the lower AUL of these hydrogels.
The third-generation superabsorbent hydrogels, which are based on poly(acrylic acid), can absorb
as much as 20-22 g/g of saline solution under a load of 4.9 kPa due to additional crosslinking on
the surface of the particles (Herbert, 1994). The first and second-generation SAPs, without these
modifications, have corresponding values of 5 g/g and ~8 g/g (Herbert, 1994). Hydrogels also
show improved AUL with higher bulk crosslinking density. By analogy, the AUL of the starch-
based hydrogels could possibly be improved by increasing the bulk crosslinking density or
introducing surface crosslinking.
32
Absorption under load (g solution/g)

8
7
6
5
4
3
2
1
0
Waxy corn starch Potato starch
Hydrogel type
Figure 3.7 Absorption under load at 4.9 kPa (0.7 psi) of hydrogels in 0.9% NaCl solution
3.4 Conclusions
Starch-based hydrogels, from potato and waxy corn starch, were prepared by aqueous
esterification reaction of starch with succinic anhydride followed by neutralization of the
substituted carboxylic acid group by alkali. The hydrogels consist of starch molecules substituted
with by ionic succinate groups and chemically crosslinked by distarch ester bond with succinic
anhydride. The absorption capacity of the hydrogels was found to be very high (>200 g/g) in water
but low in saline solution (30-40 g/g). The application of this hydrogels might be limited in
agriculture if the soil is highly saline. The absorption under load for these hydrogels (6-7 g/g) was
found to be low and similar to the first and second generation superabsorbent polymers (SAPs).
This might limit the potential of this biodegradable hydrogel to swell completely under the soil
surface. Advanced (third generation) non-biodegradable SAPs have been developed that are
augmented to withstand loads by higher bulk and/or surface crosslinking. Similarly, the absorption
under load of the starch-based hydrogel might be improved by testing different levels of
crosslinking. The hydrogels prepared from potato starch and waxy corn starch showed different
absorption properties which can be explained by the differences in their chemistry viz. the higher
phosphate group substitution in potato starch.
33
3.5 References
Buchholz, F. L., & Graham, A. T. (1998). Modern superabsorbent polymer technology. New York:
Wiley-VCH.
Chilton, W. G., & Collison, R. (1974). Hydration and gelation of modified potato starches.
International Journal of Food Science & Technology, 9(1), 87-93.
Herbert, N. (1994). Characterization of a new superabsorbent polymer generation. Superabsorbent
Polymers, 573(i), 99–111. https://doi.org/doi:10.1021/bk-1994-0573.ch008
Kabiri, K., Omidian, H., Zohuriaan‐Mehr, M. J., & Doroudiani, S. (2011). Superabsorbent
hydrogel composites and nanocomposites: aa review. Polymer Composites, 32(2), 277–
289. https://doi.org/10.1002/pc
Kazanskii, K. S., & Dubrovskii, S. A. (1992). Chemistry and physics of agricultural hydrogels.
Advances in Polymer Science, 104, 97–133. https://doi.org/10.1007/3-540-55109-3_3
Kazanskii, K. S., & Dubrovskii, S. A. (1992). Chemistry and physics of agricultural hydrogels.
Advances in Polymer Science, 104, 97–133. https://doi.org/10.1007/3-540-55109-3_3
Plastics Technology and Engineering, 50(14), 1475-1486. Laftah, W. A., Hashim, S., &
Ibrahim, A. N. (2011). Polymer hydrogels: a review.
https://doi.org/10.1080/03602559.2011.593082
Li, A., Zhang, J., & Wang, A. (2007). Utilization of starch and clay for the preparation of
superabsorbent composite, 98, 327–332. https://doi.org/10.1016/j.biortech.2005.12.026
Mao, N. (2016). Methods for characterisation of nonwoven structure, property, and performance.
In Advances in Technical Nonwovens (pp. 155-211).
Mao, N. (2016). Methods for characterization of nonwoven structure, property, and
performance. In Advances in Technical Nonwovens (pp. 155-211).
Parvathy, P. C., & Jyothi, A. N. (2012). Water sorption kinetics of superabsorbent hydrogels of
saponified cassava starch‐ graft‐ poly (acrylamide). Starch‐ Stärke, 64(10), 803-812.
Sannino, A., Maffezzoli, A., & Nicolais, L. (2003). Introduction of molecular spacers between
the crosslinks of a cellulose-based superabsorbent hydrogel: Effects on the equilibrium
sorption properties. Journal of Applied Polymer Science, 90(1), 168–174.
https://doi.org/10.1002/app.12625
34
Swinkels, J. J. M. (1985). Composition and properties of commercial native starches. Starch‐

Stärke, 37(1), 1-5.
Yoshimura, T., Matsuo, K., & Fujioka, R. (2006b). Novel biodegradable superabsorbent hydrogels
derived from cotton cellulose and succinic anhydride: Synthesis and characterization.
Journal of Applied Polymer Science, 99(6), 3251–3256. https://doi.org/10.1002/app.22794
Yoshimura, T., Yoshimura, R., Seki, C., & Fujioka, R. (2006a). Synthesis and characterization of
biodegradable hydrogels based on starch and succinic anhydride. Carbohydrate Polymers,
64(2), 345–349. https://doi.org/10.1016/j.carbpol.2005.12.023
Zohuriaan-Mehr, M. J., & Kabiri, K. (2008). Superabsorbent polymer materials: a review.
Iranian polymer journal, 17(6), 451.
35
EFFECT OF HYDROGEL SEED COATING ON EARLY

CORN GROWTH
4.1 Introduction
This chapter describes the plant growth studies that were performed to determine the effect of the
starch-based hydrogel seed coating on emergence and early growth of corn. First, a preliminary
growth study was conducted to test the effect of hydrogel film coating on seed corn germination.
Based on the results of the preliminary study, two additional growth studies were conducted that
tested the effect of two factors: hydrogel loading per seed and the available water for plant growth.
The coated seeds for this study were prepared by seed pelleting method.
4.2 Materials and Methods
4.2.1 Thin film hydrogel coating
A fixed hydrogel-seed ratio (w/w basis) was used for the coating process. This ratio was selected
based on the amount of water absorbed by a corn seed to complete germination (0.1 g) (Phillips,
1968) and the amount of hydrogel that can retain this amount of water owing to its water absorption
capacity (200 g/g, Chapter 3, Section 3.3.3). However, due to practical considerations like the
insufficiency of the calculated amount of gel to cover the whole seed surface, the process losses
and poor adhesion of gel to corn surface, an excess amount of gel was used in the coating process.
Thus, while the calculated amount of percent hydrogel per seed was 0.14% (w/w), the coating
process used 1.4% (w/w). Four batches of coated seeds with 20 seeds each were independently
prepared using identical procedure and hydrogel: seed ratio and named CH1. CH2, CH3, and CH4.
The waxy corn starch-based hydrogel (WCSH) was allowed to swell in a filter paper cone with an
excess of water for 24 h and then gravity-drained for 30 min. The obtained gel was added to dry
corn seeds in a 50 ml beaker and stirred together until the gel formed a wet film on the seeds. The
seeds were then dried at 27°C for 6 h to complete the coating process. The weight of each corn
seed batch was measured before and after the coating process to determine hydrogel deposition on
the seeds (n = 1). It is to be noted that this did not involve measuring the weight change of each
seed individually and subsequently calculating the average deposition.
36
4.2.1.1 In vitro germination study
This study involved assessing the germination and growth of hydrogel-coated corn seeds and
uncoated seeds over 10 days. One replicate of each coated seed batch (CH1 through CH4) and
uncoated seeds, with 20 seeds per replicate, were prepared. Each replicate was grown in a petri
dish and placed over four layers of paper towel. The paper towel media was irrigated using a
special scheme as described below. For the first six days, the paper towel was kept wet and dry on
alternate days. On “wet” days, 6 ml water was added to each petri dish and lidded to prevent drying.
While on “dry” days, the Petri dishes were unlidded and allowed to dry. This procedure was
followed to simulate limited water availability to seeds and to evaluate the presence of hydrogel
and its ability to retain moisture around the seeds during dry days. After 6 days, the paper towel
was kept continuously wet until complete germination to evaluate their recovery from the limited
water supply. The temperature was maintained at 22°C during this study. During the period of
germination, the laboratory RH fluctuated between 15 and 45% with an average RH of 24%.
The number of germinated seeds were counted every 24 h (Figure 4.1). A seed was considered
germinated if the radicle had protruded 2-3 mm from the seed. The germinated seeds from each
replicate were transferred to a separate petri dish so that the increased water uptake by germinated
seeds did not affect the water availability to other seeds. The Petri dishes containing the germinated
seeds were also irrigated as described above. The germination profile of the coated and uncoated
seeds was used to determine three germination indices (Baskin & Baskin, 1998) viz. time to
median germination, Timson’s index (TI), and Synchrony. They were calculated using the
equations given below:
𝑀𝑒𝑎𝑛 𝑔𝑒𝑟𝑚𝑖𝑛𝑎𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒 = ∑𝑘𝑖=1 𝑛𝑖 𝑡𝑖 / ∑𝑘𝑖=1 𝑛𝑖 (4.1)
where ni is the number of newly germinated seeds on day i, ti is the number of days after sowing,
and k is the last day of measuring germination. Time to median germination is the time at which
50% of the germinating seeds complete germination. The rate of germination is commonly defined
as the inverse of the time to median germination (Bewley et al., 2013).
𝑇𝑖𝑚𝑠𝑜𝑛′ 𝑠 𝐼𝑛𝑑𝑒𝑥 = ∑𝑘𝑖=1 𝑁𝑖 (4.2)

37
where Ni is the cumulative percent germination on day i. A higher value of this index indicates a
higher rate of germination.
𝑆𝑦𝑛𝑐ℎ𝑟𝑜𝑛𝑦 = ∑𝑘𝑖=1 𝐶𝑛𝑖 ,2 /𝑁 (4.3)
where Cni,2 is the combinations of two seeds germinating on day i, ni is the number of newly
germinated seeds on day i, and N is the total number of seeds that germinated throughout the test.
Synchrony measures the degree of overlap of germination of different seeds in a seed population.
Figure 4.1 Counting germinated seeds during in vitro germination study
4.2.2 Hydrogel coating by seed pelleting method
Seed pelleting is a technique of coating seeds that is popularly used to modify the shape, weight,
and size of small seeds by adding a large amount of inert material. Seed pelleting is primarily used
to improve their plantability but is also employed to apply seed treatment materials to the seed
(Halmer, 2008). This technique was employed in this study to dry coat seed corn with different
amounts of potato starch hydrogel (PSH). The coated seeds thus prepared were used in the second
38
and third growth study. The composition of the dry coating mixture for this process was adapted
from the method described by Su et al. (2017). Three types of hydrogel coated seeds were prepared
with the expected loadings of 1.4, 4.2 and 7.0 % (wt. hydrogel/wt. seeds). The calculated amount
of hydrogel per 20 g seeds was mixed with a 2:1 mixture of bentonite (powder, Sigma-Aldrich
#285234) and talc (powder, 10 µm; Sigma-Aldrich #243604) to a total mixture of 2.8 g. The
following table lists the composition of the powder mixtures made for various hydrogel loadings.
Table 4.1 Composition of coating powder mixture
Hydrogel seed loading Components of coating powder mixture (%)

(%) Clay Talc Hydrogel
1.4 60 30 10
4.2 47 23 30
7.0 33 17 50
In order to coat the seeds, 20 g of corn seeds were placed in a 1-quart plastic bag and added with
2 g of 1% aqueous methylcellulose adhesive solution. The mouth of the bag was sealed, and the
bag was shaken manually until all the seeds became wet with the adhesive solution. The wet seeds
were transferred to another bag containing the powder mixture and the bag was shaken again. The
corn seeds were thus coated with the powder mixture. The moist, coated seeds were dried at 40 °C
for 24 h. Some powder residue remained in the bag and did not stick to the seeds.
The amount of coating mixture deposited on the seeds was determined by measuring the change
in the individual seed weight due to the coating process (n = 20). This was used to measure the
fraction of total powder mixture used for a batch that deposited on the seeds viz. the “coating
efficiency”. The actual hydrogel loading was approximated from the observed coating efficiency
using the following equation:
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑙 𝑙𝑜𝑎𝑑𝑖𝑛𝑔 = 𝑒𝑥𝑝𝑒𝑐𝑡𝑒𝑑 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑙 𝑙𝑜𝑎𝑑𝑖𝑛𝑔 ∗ 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑎𝑡𝑖𝑛𝑔 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦⁄100

(4.4)
This assumes that all components in the powder mixture had similar adhesion to the seeds and
therefore did not segregate during the coating process.
39
4.2.2.1 Growth study in soil
This growth study was conducted to determine the effect of different levels of hydrogel coating
and different watering levels on the early growth of seed corn. The three levels of PSH coatings
prepared by seed pelleting method were tested against uncoated seeds. Three watering treatments
were applied to determine the effect of hydrogel coating on plant growth with the variation in the
amount of available water. For different watering treatments, the plants were irrigated at the same
frequency but with different amounts of water. The amount of water initially added to soil under a
treatment related to a certain fraction of its field capacity (FC). Field capacity of a soil is defined
as the amount of water retained by a soil after draining under gravity from a fully-saturated state
(Veihmeyer & Hendrickson, 1931). The three treatments levels selected were 93%, 82% and 77%
of FC. The test samples were re-irrigated to these levels when the soil water content fell to 65%
FC by evapotranspiration. In practical terms, these treatment levels supplied different amounts of
water to the plants over the drying-watering cycle. The lower limit of drying was set to 65% FC
based on the observed pattern of drying of soil under the three watering treatments. It was found
that the amount of water in all the pots converged to 65% FC after 5 days, although the initial FC
levels were different. These levels were hereafter expected to have water contents that were similar
to each other and therefore would no longer implement different water availability. And thus the
plants were watered to their respective treatment levels when 65% FC was reached.
The corn plants were grown in narrow cone-shaped pots called Deepot Cells D40L (Stuewe &
Sons, Inc., Tangent, OR, USA) with Turface MVP® calcined clay (Turface AthleticsTM) as the
growth medium. The corn seeds were sown at ~1.3 cm of depth in the soil. The plants were grown
in Conviron® E15 growth chambers (Controlled Environments Ltd., Winnipeg, Manitoba, Canada)
set to a day/night (lighted/dark) period of 16/8h and temperature of 28/23°C. The light intensity
during the day was set to 230 µmol/m2.s. The chamber RH was initially set to 60% but the soil
region near the seed was found to be drying rapidly at this RH. In order to prevent the delay of
seed emergence due to this drying, the RH of the chamber was increased to 75%. For the same
reason, the lights were also kept off. The lights were turned on after some plants began to emerge.
The soil near the seed was moistened every day with 15 ml of water for all the pots until the seeds
emerged. The different watering treatments were applied until day 21. To determine the time for
40
watering, the water level was monitored for four randomly pre-selected pots from each watering
treatment level. The amount of water added for each watering level was based on the average loss
(from the four pots) calculated from the initial water content. The water used for the study was
supplemented with 93% sulfuric acid (Brenntag, Reading, PA) at 0.08 mL/L to reduce alkalinity
to 100 mg/L and to keep pH to a range of 5.8 to 6.2. A single treatment of fertilizer solution (50
ml) was applied to all plants on day 8 (all plants had emerged) to prevent nutrition-related growth
inhibitions. The fertilizer solution contained following elements (in mg/L): 150 nitrogen, 20
Phosphorus, 122 Potassium, 38 Calcium, 15 Magnesium, 0.8 Iron, 0.4 Manganese and Zinc, 0.2
Copper and Boron, and 0.1 Molybdenum. The addition of fertilizer solution brought all the pots to
100% FC for this watering cycle and the watering treatment was restarted in the next cycle.
The emergence of corn plant from the soil surface was noted daily until all the plants had emerged.
Also, on day 14 and 21, the dry weight of root and shoot was determined for a sample of 4 plants
from each treatment combination (Figure 4.2). The plants were removed from the pots, the root
and shoot were separated and then dried at 65 °C for 3 days before weighing (Dorraji, Golchin &
Ahmadi, 2010).
Figure 4.2 Corn plant growth after 14 days of planting during the growth study
41
4.2.2.2 Emergence study in soil
Based on the results of the growth study, this study tested a more severe water stress condition (~
65% FC) against the normal watering condition (~ 92-93% FC). Under these watering conditions,
the effect of hydrogel coating (PSH) was tested on the speed of emergence of corn. The hydrogel
coating level used in this study was the highest level tested in the previous study. The seeds were
grown in the cone-shaped pots and plant growth chamber used in the previous growth study. The
chamber was set to a day/night (lighted/dark) period of 16/8h and temperature of 28/23°C. The
light intensity during the day was set to 230 µmol/m2.s. The soil surface in every pot was added
every day with 30 ml of water until the seed had emerged to compensate for: (i) rapid drying of
the soil surface and the region surrounding the seed which could completely hinder germination,
(ii) the change in the soil water content over a day. This amount was based on the gravimetric
determination of average water loss to evaporation per day (both water levels had similar water
loss) based on four randomly selected pots from each treatment combination. The emergence was
noted daily until complete emergence (Figure 4.3). The emergence profile and time to median
emergence was analyzed for the effect of the coating, watering treatment and their interaction.
Figure 4.3 Emergence of corn seeds during the emergence

42
4.2.3 Statistical analysis
The in vitro germination study investigated the effect of coating at four levels. Each level was
assigned only one replicate of 20 seeds and therefore the treatments could not be statistically
analyzed.
The growth study in soil was designed as a full-factorial study of two factors: hydrogel coating
level and watering level. Each treatment combination was applied to 10 plants, and two groups of
5 plants were arbitrarily made to act as two replicates for analysis of daily emergence data. The
percent emergence data based on these two replicates were analyzed by 2-way ANOVA (ɑ = 5%)
to determine the effect of coating level, watering level, and their possible interaction. For the
analysis of root and shoot biomass data, four plants were randomly selected from each treatment
combination as four replicates and the obtained data was analyzed using 2-way ANOVA (ɑ = 5%)
for determining the effect of hydrogel coating and watering level.
For the emergence study, a full-factorial experiment was designed with two factors – coating and
watering – with two levels each. Each treatment combination was applied to 24 seeds which were
randomly partitioned into four replicates of 8 seeds each. The daily percent emergence and time
to median emergence were thus analyzed using 2-way ANOVA (ɑ = 5%) to determine the effect
of the two factors and their possible interaction.
4.3 Results and Discussion
4.3.1 Thin film coating method
The four batches of corn seeds, coated with waxy corn starch hydrogel using the identical
procedure, were evaluated for deposition of hydrogel on the seeds by gravimetric method. The
results showed that the four batches (named CH1 through CH4) differed widely in their percent
deposition (Figure 4.4). This indicated that the thin film coating method was had high inter-batch
variability. The coating variability among the seeds of a batch or intra-batch variability was not
studied. These four batches were thereafter used in the “In vitro germination study” as four levels
of hydrogel loading to compare their germination behavior to uncoated seeds.
43
1.0
0.89
Amount of hydrogel / seed (g/100 g)

0.8
0.6 0.52
0.4 0.34
0.2 0.15
0.0
CH1 CH2 CH3 CH4
Batch
Figure 4.4 Hydrogel loading of the four batches of thin film-coated seeds (CH1-CH4) (n = 1)
4.3.1.1 In vitro germination study
The germination profile of the batches of hydrogel film-coated (CH1-4) and uncoated seeds (UC1-
4) are shown in Figure 4.5. It was observed that for the coated batches CH1 and CH2, which had
a higher hydrogel loading (0.89 and 0.52%), the onset of seed germination occurred early during
the stressed watering scheme while uncoated seeds began germination only when the water was
available continuously. The coated batches CH3 and CH4, with lower hydrogel loadings (0.15 and
0.34%), were similar to uncoated seeds in their germination response. The uncoated and coated
seeds attained ~100% germination on day 10.
The daily germination data was used to calculate the time to median germination, Timson’s index
(TI) and synchrony. The obtained values of these indices have been plotted against the amount of
hydrogel loading (0% for uncoated seeds) and are shown in Figure 4.6. The time to median
emergence was found to be lower for higher hydrogel loading. Similarly, seeds with higher loading
showed higher values of TI. These values indicate that a higher amount of hydrogel on the seeds
increased the speed of germination. However, hydrogel-coated seeds with lower loadings were
similar to uncoated seeds. As the hydrogel loading increased, synchrony index was found to
44
decrease. This indicates that the germination event in coated seeds tended to be more dispersed
over the duration of the experiment.
100 CH1 100 CH2

Percent germination, %
Uncoated Uncoated
80 80
60 60
40 40
20 20
0 0
0 2 4 6 8 10 0 2 4 6 8 10
days days
100 CH3 100 CH4

80 Uncoated 80 Uncoated
60 60
40 40
20 20
0 0
0 2 4 6 8 10 0 2 4 6 8 10
days days
Figure 4.5 Germination profile of hydrogel-coated seeds compared with uncoated seeds (n = 1)
The early germination of hydrogel-coated seeds indicates that the seeds had better access to water
during the stressed watering scheme. This may be explained by the ability of the hydrogel on the
seeds to absorb water during the wet days and to retain it for a certain duration on the dry days.
This would extend the availability of water for the coated seeds for imbibition and the seeds would
complete germination earlier. The paper towel substrate may however not retain moisture and dry
out earlier than hydrogel at the start of the dry days. Therefore, the uncoated seed would not have
water for imbibition during the dry days and would require more time for completing germination.
45
It is also likely that the seeds lost the imbibed water to the atmosphere on dry days. The drying
could have contributed to hindered germination in uncoated seeds leading to a delay in germination
until water supply became continuous. Such effects of drying were not observed for the hydrogel-
coated seeds as they continued to germinate during the stressed watering.
9.0
Mean germination time (days)
450
8.5 400
Timson's index
8.0 350
300
7.5
250
7.0 200
6.5 150
100
0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8
Hydrogel loading (%) Hydrogel loading (%)
0.60
0.55
0.50
Synchrony
0.45
0.40
0.35
0.30
0.25
0.0 0.2 0.4 0.6 0.8
Hydrogel loading (%)
Figure 4.6 Time to median germination, Timson’s and Synchrony indices plotted against
hydrogel loading (n = 1)
4.3.2 Hydrogel coating by seed pelleting method
The coating efficiency at different hydrogel compositions of the powder mixture is thus shown in
Figure 4.7. This was determined by measuring the weight change of individual seeds (n = 20) due
to the process and comparing it to the deposition per seed that is expected if all the powder had
deposited. A higher amount of hydrogel in the mixture resulted in lower coating efficiency. This
may be explained by the tendency of the hydrogel to wick away the adhesive solution present of
the seed surface, and thus reduce the potential of seed surface to bind powder mixture. Due to
46
lower coating efficiency, the hydrogel loading on the seeds would be lower than the expected
values of 1.4, 4.2 and 7.0% (Table 4.1). The actual hydrogel loading for the three coating levels is
shown in Figure 4.8.
100
90
Coating efficiency (%) 80
70
60
50
40
30
20
10
0
10% 30% 50%
Hydrogel in coating mixture (%)
Figure 4.7 Coating efficiency at different hydrogel compositions of the powder mixture (n = 20)
8.00
Observed
7.00
Expected
Hydrogel loading (% w/w)
6.00
5.00 4.2
4.00
2.6
3.00
2.00 1.1
1.00
0.00
10% 30% 50%
Hydrogel fraction in the mix (%)
Figure 4.8 Observed and expected hydrogel loading by seed pelleting method (n = 20)
47
By visual inspection of coated seeds, it was observed that the coating mixture covered the seed
surface uniformly (Figure 4.9). The seed coating was mechanically stable and did not break
under mild impact forces.
Figure 4.9 Seed corns after coating by seed pelleting method
4.3.2.1 Growth study in soil
The emergence profile for the uncoated seeds has been compared to seeds with the three levels of
hydrogel coating treatments (1.1, 2.6 and 4.2%) for the three watering levels, as presented in
Figures 4.10 - 4.12. On day 3, 4 and 5, the hydrogel-coated seeds showed signs of higher
emergence than uncoated seeds for all treatment combinations. The emergence on day 7 did not
differ between uncoated and coated seeds as almost all seeds had emerged on day 7. The 2-way
analysis of variance of daily emergence (Note: Quantile-Quantile plot showed that the data did not
satisfy the assumption of normality) showed the significant interaction of coating and watering on
day 3, 4 and 5. To study the effect of these factors closely, the coating levels were compared at
individual watering levels.
48
92-93% FC, Uncoated 92-93% FC, Uncoated

92-93% FC, Coated 1.1% 92-93% FC, Coated 2.6%
Percent emergence, %
100 100
80 80
60 60
40 40
20 20
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Day Day
92-93% FC, Uncoated
92-93% FC, Coated 4.2%
100
80
60
40
20
0
1 2 3 4 5 6 7
Day
hydrogel-coated seeds at 93% FC watering
From the post-hoc pairwise comparison (Tukey’s Honest Significance Difference test (HSD)) of
coating levels at individual watering levels, the effect of the coating was found to be most
prominent at 77% FC level. At this level, the emergence of coated seeds was higher than uncoated
seeds on day 4 with a statistically higher emergence at 2.6% hydrogel, while the all coated
treatments showed a statistical improvement in emergence over uncoated seed on day 5. The
emergence of coated and uncoated seeds did not differ statistically on day 3. At 82% FC watering,
the coating did not significantly improve emergence on any day. At 92-93% FC watering, 1.1%
hydrogel caused significantly higher emergence than uncoated on day 3, while the higher coating
levels caused slightly higher emergence on day 3. The emergence at 92-93% FC was not improved
on any other day by the coating levels. The difference between the effect of the three coating levels
was not clear from the daily emergence results.
49
At 77% FC, the time to median emergence for coated seeds (1.1, 2.6 and 4.2% levels) was
significantly lower than uncoated seeds, but similar to each other. A lower time to median
emergence indicates that the hydrogel-coated seeds emerged faster than uncoated seeds. This
indicates that the hydrogel improved the availability of water to the seeds which led to faster
germination and emergence. However, at 92-93% FC and 82% FC, the coating did not have a
significant effect on the time to median emergence.
82% FC, Uncoated 82% FC, Uncoated

82% FC, Coated 1.1% 82% FC, Coated 2.6%
100 100
80 80
60 60
40 40
20 20
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Day Day
82% FC, Uncoated
82% FC, Coated 4.2%
100
80
60
40
20
0
1 2 3 4 5 6 7
Day
50
77% FC, Uncoated 77% FC, Uncoated

77% FC, Coated 1.1% 77% FC, Coated 2.6%
100 100
80 80
60 60
40 40
20 20
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Day Day
77% FC, Uncoated
77% FC, Coated 4.2%
100
80
60
40
20
0
1 2 3 4 5 6 7
Day
The average root and shoot biomass dry weight for different coating and watering levels on days
14 and 21 were determined and are shown in Figures 4.13 – 4.16. The root dry weight was not
significantly affected by the coating or watering treatments. The shoot dry weight was affected by
watering but not by coating treatments. On day 14, the 82% FC level caused the plants to have
higher shoot weight than the 77% FC level. Similarly, on day 21, 93% FC level plants had
significantly higher shoot biomass than 77% FC level.
This shows that the hydrogel coating does not significantly affect the growth of the plant after
emergence. This can be explained by the increased plant water demand and the establishment of
an extensive root system after emergence. The roots thus provide access to water from a large
51
volume of soil while the hydrogel derives water only from a small region around the seed. The
contribution of hydrogel’s water storage capacity to the total water needs of the plant is also likely
to diminish as the plant grows.
Figure 4.13 Comparison of root and shoot dry weight of uncoated seeds and hydrogel-coated
seeds on day 14 (coating levels with the same letter are not significantly different)
(coating levels with the same letter are not significantly different)
52
Figure 4.15 Comparison of root and shoot dry weight of uncoated seeds hydrogel-coated seeds
on day 21 (coating levels with the same letter are not significantly different)
(coating levels with the same letter are not significantly different)
53
4.3.2.2 Emergence study in soil
The average emergence over 6 days for the uncoated seeds and hydrogel-coated seeds (4.2% w/w)
at the two watering levels has been summarized in Figure 4.17. There was no seed emergence in
any treatment on days 1 and 2. The daily emergence data after day 2 were analyzed using 2-way
ANOVA (ɑ = 5%) with the two factors: coating and watering.
92-93% FC, Uncoated 65% FC, Uncoated

92-93% FC, Hydrogel coated 65% FC, Hydrogel coated
100 100
80 80
60 60
40 40
20 20
0 0
1 2 3 4 5 6 7 1 2 3 4 5 6 7
Day Day
Figure 4.17 Comparison of percent daily emergence of uncoated seeds and hydrogel-coated
seeds at the two watering levels: (i) 92-93% FC, (ii) 65% FC
On day 3, the emergence was significantly affected by the interaction of watering and coating, and
the individual effects of the watering and the coating. Since the effect of the coating is likely to
differ at the two watering levels on day 3 (and approximately on other days), the different coating
levels were compared at individual watering levels. (Tukey’s HSD pairwise comparison test). At
92-93% FC watering, the hydrogel-coated seeds did not differ from uncoated seeds in daily
emergence, except for a briefly higher emergence on day 3. At 65% FC, the hydrogel-coated seeds
did not show improvement in emergence on any day. On day 4 and 5, the emergence was
significantly affected by watering level – 92-93% FC had higher emergence than 65% FC. On the
final day (day 6), the seeds reached ~100% emergence and were not significantly different for any
treatment.
54
The effect on the rate of emergence was determined by calculating the time to median emergence.
The time to median emergence was found to be similar for the hydrogel-coated and uncoated seeds,
but significantly lower at 92-93% FC (3.9 days) than 65% FC (5.0 days).
When the seed emergence results of this study were compared to the corresponding treatments of
the previous growth study (section 4.3.2.1), though the 4.2% hydrogel-coated seeds had
significantly higher emergence than uncoated seeds at 77% FC (day 5), the same was not observed
at 65% FC. This indicates that the hydrogel was not able to imbibe the required amount of water
under the more severe water stress level of 65% FC and therefore did not to influence seed
emergence. Under 92-93% FC in this study, the 4.2% coated seeds showed higher emergence than
uncoated seeds on day 3, and no improvement was seen on other days. This is unlike the results of
this watering level in the previous study that showed that 4.2% coating had no effect on any day.
This indicates that the overall effect of the coating is only minor and possibly insignificant at this
watering levels. It is concluded that the hydrogel coating did not improve emergence over uncoated
seeds if the water availability is sufficiently high (like 92-93% FC) or too low (like 65% FC). The
intermediate watering levels, like 77% FC, which may signify “moderate” water stress could
benefit from the hydrogel coating in terms of faster emergence.
4.4 Conclusions
The effect of hydrogel seed coating on the emergence of corn seeds was found to be affected by
the water availability to the seeds. At 77% FC, the median time to emergence was significantly
lower, and therefore the rate of emergence was higher, for hydrogel coated seeds than uncoated
seeds. The rate of emergence was not improved at 92-93% FC and 82% FC. Also, at the 65% FC
watering level, the rate of emergence of coated and uncoated seeds was similar. This shows that
the hydrogel coating had the most significant effect at 77% FC watering level, which may be
considered to represent “moderate” water stress during emergence. The hydrogel coating had
relatively minor or non-significant effect at “low” and “high” water stress. The rate of emergence
was significantly higher for hydrogel-coated seeds but the three coating levels were similar. This
study could therefore not determine the effect of different levels of hydrogel loading on the seeds.
In the light of these effects on the emergence results, it can be concluded that the hydrogel coating
had the effect of accelerating the emergence of seed corn. This may be explained by higher and
55
prolonged access to moisture by the seed due to the absorption and retention of water by the
hydrogel coating. From the study of the dry biomass accumulation by the corn plants after 14 and
21 days, it was observed that the hydrogel coating did not have a significant effect on the vegetative
growth of the plant after emergence. This may be explained by the development of extensive roots
by the plant after emergence, which allows the plant to access soil water more effectively. The
contribution of the coating to the plant’s water needs is seemingly diminished due to low total
capacity and a small region of access.
4.5 References
Baskin, C. C., & Baskin, J. M. (2014). Ecologically meaningful germination studies. Seeds.
https://doi.org/10.1016/B978-0-12-416677-6.00002-0
Bewley J.D., Bradford K.J., Hilhorst H.W.M., Nonogaki H. (2013) Germination. In: Seeds.
Springer, New York, NY
Dorraji, S. S., Golchin, A., & Ahmadi, S. (2010). The effects of hydrophilic polymer and soil
salinity on corn growth in sandy and loamy soils. Clean - Soil, Air, Water.
https://doi.org/10.1002/clen.201000017
Halmer, P. (2008). Seed technology and seed enhancement. Acta Horticulturae, 771(2), 17–26.
Phillips, R. E. (1968). Water diffusivity of germinating soybean, corn, and cotton seed. Agronomy
Journal, 60(5), 568–571.
Rundle, R. E., Foster, J. F., & Baldwin, R. R. (1944). On the nature of the starch-iodine complex.
Journal of the American Chemical Society, 66(12), 2116–2120.
https://doi.org/10.1021/ja01240a031
Su, L., Li, J., Xue, H., & Wang, X.-F. (2017). Super absorbent polymer seed coatings promote
seed germination and seedling growth of Caragana korshinskii in drought. Journal of
Zhejiang University-SCIENCE B, 18(8), 696–706. https://doi.org/10.1631/jzus.B1600350
Veihmeyer, F. J., & Hendrickson, A. H. (1931). The moisture equivalent as a measure of the field
capacity of soils. Soil Science. https://doi.org/10.1097/00010694-193109000-00003
56
OVERALL CONCLUSIONS AND FUTURE WORK
5.1 Restatement of the thesis objectives
The objective of this research project was to understand the behavior of hydrogel seed coating in
terms of its ability to improve water availability to a seed during its early growth. Seeds are
susceptible to hindered germination in a soil where water availability is limited by dry weather or
limited irrigation resources. Low germination is mainly due to a limited area of contact of the seed
with the soil and the requirement of prolonged water availability in the proximity of seed for
germination. The effect of hydrogel coating depends on a number of factors: the seed species, the
nature of the hydrogel, the amount of hydrogel on the seed, the method of coating and associated
coating formulations, and the amount of water in the soil. In this work, the effect of two factors -
the amount of hydrogel on the seed and the amount of water in the soil – were studied for a given
system of seed species (corn) and hydrogel material through a series of plant growth experiments.
Another purpose of this research was to determine the suitability and efficacy of a biodegradable
starch-based hydrogel for application in agricultural water management. As part of this objective,
the hydrogel was characterized by its various water absorption properties. The effect of starch-
based hydrogel on water management was also determined based on the growth experiments
conducted using the hydrogel as a seed coating material.
5.2 Conclusions on the absorption properties of the hydrogel
Although the potato starch-based hydrogel had high absorption capacity in distilled water (260
g/g), the corresponding absorption with a standard saline solution (0.9% by weight sodium
hydroxide) was low at 30 g/g. Under an indicated load of 4.9 kPa in saline solution, the absorption
capacity further reduced to 7 g/g. This indicated a limited tolerance to osmotic and mechanical
stresses that might be encountered in the soil during agricultural application. However, these
values are close to those for first and second generation of poly(acrylic acid)-based superabsorbent
materials. These properties may be enhanced by optimizing the preparation procedure, particularly
by improving the bulk and surface crosslinking profile. It may be noted that these properties are
considered standard measures of the absorption behavior for the application of superabsorbent
57
polymers in disposable hygiene products. The absorption requirements can, however, vary widely
in agriculture due to variations in soil salinity, fertilizer content, soil texture and soil density. The
prediction of performance of the hydrogel in a certain environment would require testing the
hydrogel under the relevant chemical, osmotic and mechanical factors.
5.3 Conclusions on the effect of hydrogel coating on corn plant growth
The effect of hydrogel seed coating on the growth of corn seeds was found to be significantly
dependent on two factors - the amount of hydrogel on the seed and the amount of water in the soil.
The hydrogel improved the seed emergence under watering conditions that applied moderate water
stress. The emergence of seeds was not significantly affected by the hydrogel coating when the
soil had the adequately high amount of water (> 82% of field capacity) or when the soil water level
was too low (<65% of field capacity). This shows that the hydrogel coating improved the
availability of water for imbibition and therefore the resulting rate of germination in corn seeds,
but only at a moderate level of water stress. The rate of emergence was significantly higher for
hydrogel-coated seeds, but the three coating levels were similar. This study could therefore not
determine the effect of different levels of hydrogel loading on the seeds. The post-emergence
growth of the corn plant was not significantly affected by the coating. This indicates that the
coating’s contribution to plant water needs becomes insignificant as the plant becomes capable of
deriving soil water from a wider region and in larger amounts via its roots.
5.4 Future work
Even the best efforts of a research project can leave some stones unturned. This study is no
exception. The future work can be an opportunity to not only build on the findings of this study
and to refine it, but also to change the methodologies to make them more robust to variabilities
inherent to the systems under investigation.
The study did not investigate the inter-batch variability of the hydrogel product. It was assumed
that the hydrogel product from different batches did not differ significantly in its chemical and
physical properties. Under this assumption, different hydrogel characterization procedures and
growth studies were conducted using hydrogel from different batches. It is, however, important to
58
verify this assumption so that a representative estimate of the properties and the effects of the
hydrogel can be made. It is also recommended to derive hydrogel samples for different
experiments from a composite sample that is prepared by mixing different batches of the hydrogel.
The effect of talc and clay present in the hydrogel coating may be important to the results of the
relevant growth study. In the growth analysis of seeds that were coated with hydrogel by seed
pelleting method, the effect of clay and talc was assumed to be negligible as this was found by Su
Li, Xue & Wang (2017) in their study on similarly coated seeds. However, the composition of
these materials in the coating is more widely variable in the current study than in Su et al. (2017).
Moreover, the amounts of these materials are comparable to the total amount of hydrogel in the
coating, unlike the referred study where talc and clay were in relative excess. Due to this, it is
important to check the effect of these additives and how they could interfere with the effect of the
hydrogel.
The seed pelleting method may be checked for variability in the deposition of the hydrogel among
the seeds. The evaluation of total powder loading in this study showed a low variability among
individual seeds. The amount of hydrogel loading was however assumed to correspond to the total
powder loading and the original hydrogel composition in the powder mixture. It may be important
to verify this assumption experimentally. This variability is important to establish a significant
difference in the intended application of “different” coating levels.
In future, the coating levels may be selected to have a wider range to improve the resolution of the
effect of different levels. The coating levels selected in this study may be too close to study the
effect of the different amount of hydrogel on the seeds.
Using more replicates per treatment and more plants per replicate for seed emergence data
collection, so that the treatments can be compared more accurately: In future, the conclusions of
this study may be refined by conducting a study with a higher number of replications of each
treatment. In particular, measurement of daily emergence requires each replication to have several
seeds. The daily percent emergence of each replicate is calculated based on the fraction of seeds
that emerge in this group. This number has been kept below 10 in the current study due to practical
59
considerations like the limited space in growth chambers, the high amount of materials required
and the amount of time required for each application (daily) the watering regimes to all the plants.
However, it is normal to use more than 20 plants per replicate in the published studies. The data
from a higher number of seeds could provide a better resolution of treatment effects.
Fungal growth was observed after 14 days on the surface of hydrogel-coated seeds during the seed
growth experiments. This could have reduced the effective amount of hydrogel on the seeds. This
was however not accounted in the results of this study. In future, a study on microbial degradation
kinetics of the hydrogel and associated loss of absorption property can give insights into the
maximum life of hydrogel in the soil. The growth experiments could be improved by using
sanitized seeds and adding a small amount of microbial growth inhibitor to the prepared hydrogel
before application.
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Effect of Starch-Based Hydrogel On Early Growth of Corn

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Effect of Starch-Based Hydrogel On Early Growth of Corn

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Purdue University

Open Access Theses Theses and Dissertations

Effect of Starch-based Hydrogel on Early Growth of Corn

Follow this and additional works at: https://docs.lib.purdue.edu/open_access_theses

Master of Science in Agricultural and Biological Engineering

School of Agricultural & Biological Engineering

THE PURDUE UNIVERSITY GRADUATE SCHOOL

Dr. Rose Prabin Kingsly Ambrose, Chair

Dedicated to Maa, Papa, and Tanya

LIST OF TABLES ......................................................................................................................... ix

3.2.2 Fourier transform-infrared spectroscopy (FT-IR) ..................................................... 24

Table 4.1 Composition of coating powder mixture ...................................................................... 38

Figure 3.1 Procedure of hydrogel preparation .............................................................................. 24

AANa Sodium acrylate

Author: Pathak, Vaibhav. MS

Hydrogels or superabsorbent hydrogels are hydrophilic three-dimensional network polymers that

1.2 Hydrogels from Natural Polymers

1.3 Application of Hydrogel in Agriculture

1.4 Project overview

2.1 Hydrogels and their preparation

2.1.1 Properties of hydrogels and their applications

2.1.2 Classification of Hydrogels based on Crosslinking Bonds

2.1.3 Theory of water absorption by hydrogels

2.2 Chemistry of Commercial Superabsorbent Hydrogels

2.3 Drawbacks of Synthetic Superabsorbent Hydrogels

2.4 Superabsorbent Hydrogels Prepared Using Polysaccharides

starch. It was prepared by a free radical graft copolymerization of acrylonitrile monomer on

2.5 Polysaccharide-based Hydrogels

Yoshimura et al. (2006a) prepared a superabsorbent polymer from cotton cellulose by an

2.6 Application of Superabsorbent Hydrogel in Agriculture

2.6.1 Seed Germination and Water Uptake

2.6.2 Soil Amendment with Hydrogel

2.6.3 Seed Treatment with Hydrogel

PREPARATION AND PROPERTIES OF STARCH-

3.2 Materials and Methods

3.2.1 Preparation of hydrogel

𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠

Figure 3.1 Procedure of hydrogel preparation

3.2.2 Fourier transform-infrared spectroscopy (FT-IR)

3.2.3 Water absorption capacity

weight of swollen hydrogel−weight of dry hydrogel

3.2.4 Absorption under load

weight of swollen hydrogel under load−weight of dry hydrogel

Figure 3.3 Schematic of the apparatus used for measuring Absorption-under-load

3.2.5 Statistical analysis

3.3 Results and Discussion

3.3.1 Preparation of hydrogel

3.3.2 Fourier Transform-Infrared Spectroscopy (FT-IR)

1550 cm-1 1735 cm-1

Waxy corn starch hydrogel

0 500 1000 1500 2000 2500 3000 3500 4000 4500

1550 cm-1 1735 cm-1

Potato starch hydrogel

0 500 1000 1500 2000 2500 3000 3500 4000 4500

3.3.3 Water Absorption Capacity

Distilled water 0.9% NaCl Distilled water 0.9% NaCl

Water absorption capacity (g/g)

a) Final dry weight basis b) Initial dry weight basis

3.3.4 Absorption under load

Absorption under load (g solution/g)

Swinkels, J. J. M. (1985). Composition and properties of commercial native starches. Starch‐

EFFECT OF HYDROGEL SEED COATING ON EARLY

4.2 Materials and Methods