HYDROGEL LAB REPORT

Polymer engineering

MARCH 26, 2018

THE BRITISH UNIVERSITY IN EGYPT
Yasser ashour 127978
Abstract
The aim of this experiment is to prepare hydrogel using a monomer of 2-Acrylamido -2-
Methyl- 1-Propane Sulphonic Acid (AMPS) with the cross-linking agent Methylene-bis-
acrylamide that have a concentration of 0.15 under the suitable temperature needed to
produce a hydrogel. After that, the hydrogel is passed through N2 for the removal oxygen
then within the applied heat from the oven the hydrogel will be ready for usage after certain
time. Moreover, the samples are collected and then tested with distilled water and salty
water to find out which one will have the highest rate of production. Finally, after conducting
the experiment it was observed that the rate of absorption for distilled water by the hydrogel
is larger than the rate of absorption of the salty water.
Contents
Abstract ...................................................................................................................................... 0
Introduction ............................................................................................................................... 5
History .................................................................................................................................... 5
Physical and chemical properties .......................................................................................... 6
Swelling .............................................................................................................................. 6
Mechanical properties ........................................................................................................... 8
Applications............................................................................................................................ 8
Domestic uses .................................................................................................................... 8
Diapers ............................................................................................................................... 8
Watering beads .................................................................................................................. 9
Plastic surgery .................................................................................................................... 9
Environmental applications ............................................................................................. 10
Bacterial culture ............................................................................................................... 10
Drug delivery applications ............................................................................................... 11
Materials and procedures ........................................................................................................ 11
Results and discussion ............................................................................................................. 12
For tape water...................................................................................................................... 13
For salty water ..................................................................................................................... 14
Comparing rate of absorption between tape water and distilled water ............................ 16
Conclusions and Errors ............................................................................................................ 18
References ............................................................................................................................... 18
Table of figures

Figure 1 .................................................................................................................................... 14
Figure 2 .................................................................................................................................... 14
Figure 3 .................................................................................................................................... 15
Figure 4 .................................................................................................................................... 16
Figure 5 .................................................................................................................................... 17
Figure 6 .................................................................................................................................... 17
Table of tables
Table 1 ...................................................................................................................................... 12
Table 2 ...................................................................................................................................... 13
Table 3 ...................................................................................................................................... 15
Table 4 ...................................................................................................................................... 16
Introduction
Hydrogels are polymers that can retain many times their own weight in water. They are often
polymers of carboxylic acids. The acid groups ionize in water, leaving the polymer with several
negative charges along its length. This has two effects. Firstly, the negative charges repel each
other, and the polymer is forced to expand. Secondly, polar water molecules are attracted to
the negative charges. This increases the viscosity of the resulting mixture because the
polymer chain now takes up more space and resists the flow of solvent molecules around it.

The polymer is in equilibrium with the water around it, but the equilibrium can be disturbed
in several ways. If the the ionic concentration of the solution is increased, for example by
adding salt, the positive ions attach themselves to the negative sites on the polymer,
effectively neutralizing the charges. This causes the polymer to collapse in on itself again.
Adding alkali removes the acid ions and causes the position of equilibrium to move to the
right; adding acid has the opposite effect. There are many hydrogels and they expand and
contract at different pH values, temperatures and ionic concentrations. By using a mixture of
monomers to create the polymer these characteristics can be fine-tuned. The commonly
available hydrogels that are suggested for use in this practical activity are sensitive to salt
concentration but do not show much change across the pH range which can be investigated
readily in the classroom. They lend themselves very well to a range of investigative practical
work. For example, their volume in different amounts of water or in different salt
concentrations could be measured.
(J, 2002)

History
The word “hydrogel”, according to Lee, Kwon and Park, dates to an article published in 1894.
Anyway, the material described there was not a hydrogel as we describe it today; it was
indeed a colloidal gel made with inorganic salts. Is yet remarkable to notice how the history
of the term itself is consistently long. Anyhow, the first crosslinked network material that
appeared in literature and has been described by its typical hydrogel properties, one for all
the high water affinity, was a polyhydroxyethylmethacrylate (pHEMA) hydrogel developed
much later, in 1960, with the ambitious goal of using them in permanent contact applications
with human tissues, hydrogels are in fact the first materials developed for uses inside the
patient. Since then the number of studies about hydrogels for biomedical applications began
to rise, especially from the decade of 70's. The aims and goals and the number of materials
changed and enlarged constantly over the years. As suggested by Buwalda et al., the history
of hydrogels can be divided in three main blocks. A hydrogel’s first generation that comprises
a wide range of crosslinking procedures involving the chemical modifications of a monomer
or polymer with an initiator. The general aim is to develop material with high swelling, good
mechanical properties and relatively simple rationale. Then, starting in the seventies, a
different concept of hydrogel grew in importance: a second generation of materials capable
of a response to specific stimuli, such as variations in temperature, pH or concentration of
specific molecules in solution. These specific stimuli can be exploited to trigger likewise
specific events, for example the polymerization of the material, a drug delivery or an in-
situ pore formation. Finally, a third generation of hydrogels focusing on the investigation and
development of stereo complexed materials hydrogels cross linked by other physical
interactions (e.g. cyclodextrines). This progress in hydrogel’s science is quickly leading to an
increasing interest in the development of the so called “smart hydrogels”, polymeric matrixes
with a wide spectrum of tuneable properties and trigger stimuli. The topic is theoretically
inexhaustible and the possible applications, the engineering and medical devices that can be
obtained from it are above any imagination. Since the pioneering work of Wichterle and Lim
in 1960 on crosslinked hydrogels, and because of their hydrophilic character and potential to
be biocompatible, hydrogels have been of great interest to biomaterial scientists for many
years. The important and influential work of Lim and Sun in 1980 demonstrated the successful
application of calcium alginate microcapsules for cell encapsulation. Later in the 1980s,
Yannas and coworkers incorporated natural polymers such as collagen and shark cartilage
into hydrogels for use as artificial burn dressings. Hydrogels based on both natural and
synthetic polymers have continued to be of interest for encapsulation of cells and most
recently such hydrogels have become especially attractive to the new field of “tissue
engineering” as matrices for repairing and regenerating a wide variety of tissues and organs.
(SC, 2013)

Physical and chemical properties

Swelling
Hydrogels are cross-linked polymer networks swollen in a liquid medium. The imbibed liquid
serves as a selective filter to allow free diffusion of some solute molecules, while the polymer
network serves as a matrix to hold the liquid together. Hydrogels may absorb from 10-20%
(an arbitrary lower limit) up to thousands of times their dry weight in water. The character of
the water in a hydrogel can determine the overall permeation of nutrients into and cellular
products out of the gel. When a dry hydrogel begins to absorb water, the first water molecules
entering the matrix will hydrate the most polar, hydrophilic groups, leading to primary bound
water. As the polar groups are hydrated, the network swells, and exposes hydrophobic
groups, which also interact with water molecules, leading to hydrophobically-bound water,
or secondary bound water. Primary and secondary bound water are often combined and
simply called the total bound water. After the polar and hydrophobic sites have interacted
with and bound water molecules, the network will imbibe additional water, due to the
osmotic driving force of the network chains towards infinite dilution. This additional swelling
is opposed by the covalent or physical crosslink, leading to an elastic network retraction force.
Thus, the hydrogel will reach an equilibrium swelling level. The additional swelling water that
is imbibed after the ionic, polar and hydrophobic groups become saturated with bound water
is called free water or bulk water and is assumed to fill the space between the network chains,
and/or the centre of larger pores, micropores or voids. As the network swells, if the network
chains or crosslink are degradable, the gel will begin to disintegrate and dissolve, at a rate
depending on its composition.There are a few methods used by researchers to estimate the
relative amounts of free and bound water, as fractions of the total water content. All of them
are controversial, since there is proton NMR evidence that the interchange of water
molecules between the so-called bound and free states is extremely rapid, perhaps as fast as
one H2O molecule every 10-9s. The three major methods used to characterize water in
hydrogels are based on the use of small molecular probes, DSC and NMR. When probe
molecules are used, the labeled probe solution is equilibrated with the hydrogel, and the
concentration of the probe molecule in the gel at equilibrium is measured. If only the free
water in the gel can dissolve the probe solute, one can calculate the free water content from
the amount of the imbibed probe molecule and the known (measured) probe molecule
concentration in the external solution. Then the bound water is obtained by difference of the
measured total water content of the hydrogel and the calculated free water content. The use
of DSC assumes that only the free water may be frozen, so it is assumed that the endotherm
measured when warming the frozen gel represents the melting of the free water, and that
value will yield the amount of free water in the HG sample being tested. Then the bound
water is obtained by difference of the measured total water content of the HG test specimen,
and the calculated free water content. In another formulation, swelling is the property to
absorb water and retain it for a relative long time. It can be evaluated by measuring the dry
weight and the swollen-state weight and computing either a ponderal variation (water
uptake) or a volume of adsorbed solvent (both the quantities are considered as percentages).

As simple as it may seem, the evaluation of swelling is the principal assay to be performed on
hydrogel samples, as it can be a measure for many of their properties: crosslinking degree,
mechanical properties, degradation rate and so on. For many gels, the evaluation of swelling
and swollen state stability is the simplest, cheapest and surest way to discriminate between
crosslinked gels and the not crosslinked original polymer.
(Centre, 2007)
Mechanical properties

The mechanical properties can vary and be tuned depending on the purpose of the material.
It is possible to obtain a gel with higher stiffness increasing the crosslinking degree or lowering
it by heating the material. The changes in mechanical properties link to a wide range of
variables and causes and different analysis must be made according to the material, the
conditions and the aim of the study. For example, while gelatine show a noticeable increase
in Young Modulus through crosslinking, silk fibroin has a very high Young Modulus, but after
the revitalization it will decrease. These properties (young modulus, Poisson modulus, storage
and loss moduli, tanδ) can be evaluated by a Dynamic Mechanical Analysis (DMA) device or a
rheometer.
(J, 2002)

Applications

Domestic uses
It’s not mandatory for life changing inventions to be high-tech devices with out-of-sight
ambitions. Sometimes the simplest expedient can lead to a bigger progress than expensive
and futuristic technologies. This is true for hydrogels, too. This class of materials has plenty of
domestic usages that exploit their ability of loading, retaining and releasing fluids to
significantly improve everyday life.
(K, 1998)
Diapers
An interesting application of hydrogel’s thermodynamically affinity for water, as not fancy as
it can be, is the production of super-adsorbent diapers with the property of being dry even
after a considerable adsorption of fluids. This is due to the nature of hydrogel’s water
adsorption: these materials don’t act as sponges, unstably trapping liquids into their pores,
but instead they retain water (or, sometimes, other solvents) in while if they are carrying
considerable quantities of water at the same time. The development of hydrogel-containing
diapers, most of them loaded with different formulations of sodium polyacrylate, in the past
two decades cut down on a huge number of dermatological conditions related to a prolonged
contact with wet tissues. Indeed, many chemicals used in the production of such products,
like scents, leak-proof materials and super-adsorbent polymers, seem to be key elements for
the development of many conditions, from chronic diaper rash and asthma, to more serious
problems such as male infertility or even testicular cancer. Furthermore, disposable diapers,
since they are used in huge quantity, create a notable environmental issue since it’s not easy
to dispose of them.
(K, 1998)
Watering beads
Another simple application of hydrogels consists in rough powders of polyacrylamide or
potassium polyacrylatematrix sold with a huge range of names (Plant-Gel, Super Crystals,
Water-Gel Crystals) and used as long-term reservoir of water for plant growth in gardening,
domestic and sometimes industrial horticulture. On the opposite side as the one of diaper’s
hydrogel, these materials are optimized for their ability of releasing water, instead of the
ability of retaining it. The sustained release of many diverse species is, indeed, one of the
main strength of hydrogels on the market, from gardening to genetic engineering. However,
even if companies producing such crystals are promoting their practicality and versatility, in
the last years the scientific community is questioning about their real utility. As Chalker-Scott
from Washington State University pointed out in her publications on the topic, since the
commonly used watering crystals are made out of non-renewable materials, whose
monomers can be toxic (e.g. acrylamide), the potential risks of their usage are way higher
than the benefits of water storage and controlled release that can, in addition, be obtained
in many other ways with lower environmental impact .
(Raju KM, Synthesis of novel superabsorbing copolymers for agriculture, 2001)

Plastic surgery

From their first development into the scientific research field, hydrogel where seen as good
materials for application in contact with the human body because of their extracellular matrix.
This is the main reason why attempts were made to introduce hydrogels like new materials
for plastic reconstruction. On this path, for many years, Hyaluronic Acid (HA) was thought like
the panacea for every pain. Is not surprising, considered this, that HA has been studied to be
applied in tissue filling applications. One notable company operating in the field is
MacrolaneTM Starting in 2008, Macrolane’s treatments and products were specifically studied
to enhance breast size and shape and offer a more biocompatible alternative to standard and
aggressive silicone prosthesis. Anyhow, soon the scientific community started to point out
the controversial behaviour of these procedures in latter mammography’s: briefly, HA worked
as a shielding agent, appearing as denser tissue, and consequently ruining the outcome of the
exam. Thus, nowadays MacrolaneTM is used for diversely situated filling with the exception of
breasts. The compound is injected inside the body with a syringe and let it gels restoring the
volume. Another promising use of hydrogels is bulking agents for treatment of urinary
incontinence: smart injectable gels can be involved in clinical procedures where these
materials can be used to tighten the urethral channel and reduce patient’s incontinence. With
such a simple solution it is possible to erase or at least reduce a consistent social handicap
and help patients to hold a normal life. An example of product used in this field is Bulkamid® by
Contura International, a polyacrylamide hydrogel is a commercial product developed to help
women with incontinence narrowing the conduct. There are few motive for the incontinence,
and an exhaustive classification is made by Lose et al. where they subdivide each class,
Bladder / Urethra incontinent, in overactivity / underactivity, in their work they wrote that
bulk injectable systems are promising to improve urethral coaptation. Problematics like
infections and body response have been evaluated. In a sample composed by 130 women
researchers have found 10 patients with infections, 5 with injection site pain, 2 with
incontinence and only 1 with injection site laceration.
(Jinsub, 1986)
Environmental applications

Over past the years, nations gradually started to care about environmental issues and
pollution. Many governments decided to opt for greener and safer for the environment
policies. Water pollution is one of the biggest issues afflicting especially poor areas of Africa,
Asia and South America. Thanks to their affinity for water, hydrogels might be used in two
different ways to treat water source.
First the matrix can be used as a holder for purifying microorganism. Many interesting studies,
on this particular path, were developed by encapsulating microorganisms inside diverse
carrier materials. Chlorella and Spirulina are the most used ones. These microorganisms are
already used to remove pollutants chemicals from water resources. The idea is to keep the
bacteria inside the network and consequently protect and control the bacteria-colturewhile
cleaning the site of depuration. Both synthetic and natural hydrogels where been used. The
best working hydrogels in literature appear to be Alginate derived or alternatively
carrageenan and agar.

A second interesting way to solve the problem of pollutants is to modify the hydrogels to let
them seize and keep the pollutant inside the networks. Many methods have tried this way to
seize metal ions: the group of Irani has sent to publish a paper in which they discuss a new
composite hydrogel for PbI(II) removal. Briefly, they created a polyethylene-g-poly (acrylic
acid)-co-starch/ OMMT (LLDPE-g-PAA-co-starch/OMMT) hydrogel composite, using it like an
adsorbent pollutant (Pb(II)) remover. They put the hydrogel in a solution containing lead
acetate and then measured the adsorption with an Atomic Absorption Spectrometer (AAS);
after that they did a de-absorption phase and repeat for several cycles. The electrostatic
attractions, ion exchange and chelation are possible explanation for the metal adsorption
happened during the experiments. They reported that the equilibrium adsorption data of the
hydrogel was consistent with Langmuir isotherm and the 430mg/g adsorption capacity was in
line with other common adsorbents.
(Raju KM, Synthesis of novel superabsorbing, 2001)

Bacterial culture
hydrogels can hold inside their matrix a significant number of microorganism for purification
of water, for production of biomolecules, or for simple culture of bacteria by themselves.
Indeed, agar is famous as the golden standard substrate for bacterial culture in
biotechnological applications. Since it is indigestible by a great number of bacteria and
microorganism, it provides a perfect environment for their culture on a solid substrate.
Different kinds of agar are being studied, each with a potential use for likewise different kinds
of bacterial. Between them Brucella agar, columbic agar, schaedler agar, or trypicasesoy agar
are the most common. None of these gels hassuperior results compared to the others, instead
everyone is suitable for different applications in reason of their different pros and their cons.
(Khoylou F, 2009)

Drug delivery applications

By drug delivery we intend the whole ensemble of procedures, devices and techniques to
avoid the problems of standard delivery of medicals, first the burst release and quick decay
of the effects of the drug overtime, especially for short half-life pharmaceuticals. Hydrogels,
and smart hydrogels, can be a very interesting solution in reaching a sustained and targeted
release of pharmaceuticals, both increasing the effect of the drug itself and lowering side
effects at the same time. Silk Fibroin, protein-based biomaterial with high Young Modulus (1-
10GPa) obtained processing the silk from various insects, like spider or silk worm (Bombyx
Mori). The silk fiber is composed by fibroin and sericine. This second protein is correlated with
inflammatory reactions when coupled with fibroin. To obtain a pure fibroin wire, silk is boiled
in alkaline solution at 120° C for at least 1 hour. Solubilization and regeneration is necessary
for use this biomaterial for tissue engineering, like scaffolding. Usually the fibroin is processed
in a solution of LiBr , in a ternary solvent composed by Calcium Chloride / Ethanol / Water to
break fiber to fiber bond or by SDS . This allows the casting of the polymer and the consequent
creation of different structure for geometrical complexity. In 2011 Chinmoy et Al. used silk
fibroin from Bombyx Mori and from NathereaMylitta to create a 3D scaffold for cardiac tissue
engineering. Results showed that metabolic cell response, cardiomyocytes growth and the
number of junction between cells for AntheraeaMylitta fibroin are very similar to fibronectin
ones. They concluded that silk fibroin from AM enables an efficient attachment of cells
without affecting their response to extracellular stimuli. (M, 2011)

Materials and procedures

 -AMPS, Monomer.
 -Methylene-bis-acrylamide, cross linker.
 -Ammonium Persulphate, initiator.
 -Nitrogen or Argon or helium to get rid of air and provide inert blanket.
 -Distilled water.
 -Oven.
 -200mlground joint conical flask.
 -3Test tubes with cork.

First of all, Place25 ml of distilled water in a suitable conical flask then add 10 g of (AMPS)
with 0.15 gm of the cross-linking agent which is Methylene-bis-acrylamide and then shake
well. After finishing the previous step Pass N2 or Helium to get rid of oxygen from the solution
to avoid any deformation in the production of hydrogel or any defects that may cause the
rate of absorption of water by the hydrogel. After passing the hydrogel through N2 quickly
Add about 0.02 g of the initiator then shake well. Finally, Pour the solution into test tubes
covered with suitable cork and replace in oven for 1:2 hours at 600 C. after ensuring that he
hydrogel is ready to be used, the samples are taken out and then they are divided into suitable
discs with known weights to be examined by different solution such as salty water and
distilled water to find out the rate of absorption in both mediums.

Results and discussion

Methylene-bis-acrylamide (cross linking agent) =0.15 gm
Sample 1 = 3.13 gram (salty water)
Sample 2 = 2.05 grams (tape water)
Table 1

Time Sample 1 (salty water) Sample 2 (tape water)

0 100 initial volume of water 200 initial volume of water
2 95 190
4 92 182
6 90 180
8 87 177
10 85 175
15 82 172
20 80 170
25 78 168
30 76 165
40 74 163
48 72 161

After cutting the hydrogel into two pieces each one have to be weighted using sensitive
balance. According to what we did in this experiment sample 1 that weights 2.05 grams was
tested in a tape water to discover the rate of its absorption while the other one which weights
3.13 grams was tested using salty water that has been prepared in the lab using 5 gm of salt
and 100 ml of distilled water. According to the above results for the first sample which was
immersed in the tap water, the rate of absorption for the first 10 hours was 25 ml/ 10 hours
as this sample had absorbed for its first two hours bout 10 ml from total volume of water in
the beaker. However, after passing 10 hours from immersing the hydrogel into the tap water
the rate of absorption decreases gradually with the time. The absorption rate for the water
by the hydrogel mainly depend on the cross-linking agent used for preparing the hydrogel as
if the cross-linking agent increases the chains will be highly joined with each other resulting
in hardness and low absorption rate but while if the cross-linking agent decreases the
absorption rate will increase but the hydrogel itself will become more fragile.
For tape water
Mass of sample=2.05
Y=2.05*25/35=1.46
X=2.05*10/35=0.59

Table 2

time Volume volume of water/ unit monomer ( tape water) Accumulated

absorbed volume tape
water
0 0 2.5 2.5
2 10 19.42 21.92
4 8 16.03 37.95
6 2 5.86 43.81
8 3 7.55 51.36
10 2 5.86 57.22
15 3 7.55 64.77
20 2 5.86 70.63
25 2 5.86 76.49
30 3 7.55 84.04
40 2 5.86 89.9
48 2 5.86 95.76
 tape water
25

20

15

10

0
0 10 20 30 40 50 60

Figure 1

Accumulated volume using tape water

120

100

80
volume

60

40

20

0
0 10 20 30 40 50 60
time

Figure 2

For salty water

Mass of sample=3.13
Y=3.13*25/35=2.24
X=3.13*10/35=0.894

Table 3

time Volume of water volume of water/ unit monomer ( salty Accumulated

absorbed water ) volume salty
0 0 2.5 2.5
2 5 8.09 10.59
4 3 5.86 16.45
6 2 4.74 21.19
8 3 5.86 27.05
10 2 4.74 31.79
15 2 4.74 36.53
20 3 5.86 42.39
25 2 4.74 47.13
30 2 4.74 51.87
40 2 4.74 56.61
48 2 4.74 61.35

salty water
9
8
7
6
5
4
3
2
1
0
0 10 20 30 40 50 60

Figure 3
 Accumulated volume using salty water
70

60

50
volume

40

30

20

10

0
0 10 20 30 40 50 60
time

Figure 4

Comparing rate of absorption between tape water and distilled water

Table 4

time Volume/unit Volume/unit Accumulated Accumulated

monomer salty monomer distilled volume for volume for
tape water salty water
0 2.5 2.5 2.5 2.5
2 8.09 19.42 21.92 10.59
4 5.86 16.03 37.95 16.45
6 4.74 5.86 43.81 21.19
8 5.86 7.55 51.36 27.05
10 4.74 5.86 57.22 31.79
15 4.74 7.55 64.77 36.53
20 5.86 5.86 70.63 42.39
25 4.74 5.86 76.49 47.13
30 4.74 7.55 84.04 51.87
40 4.74 5.86 89.9 56.61
48 4.74 5.86 95.76 61.35
 25

20

15

10

0
0 10 20 30 40 50 60

salty tape

Figure 5

tape water vs salty water

120

100

80
volume

60

40

20

0
0 10 20 30 40 50 60
time

Accumulated volume salty water Accumulated volume tape water

Figure 6

hydrogels when they are partially crosslinked and can absorb water through hydrogen
bonding. The ability to absorb water is related to the ionic concentration of the water used.
The greatest amount that can be absorbed is in distilled water where it can reach 500 times
its own weight, or 30 to 60 times its own volume. As an example, if salt water is used the
polymer will not swell as the ionic balance has been shifted. So, the anionic or cationic, (minus
or plus charge), determines how the polymer will react. There is also a relationship between
how crosslinked the polymer might be and its swelling capacity. Low density crosslinked
polymers swell to a larger degree but have a softer and more fragile gel structure. The spheres
in the video are quite fragile and will break apart easily when fully loaded with water. Higher
crosslinked polymers show less absorption but can maintain their shape and firmness under
pressure.
Conclusions and Errors
To conclude, the purpose of this experiment is to prepare the hydrogel and also to examine
its rate of absorption through different mediums such as distilled water and salty water and
it was found that the rate of absorption of the distilled water by the hydrogel is larger than
the rate of absorption of the salty water due to anionic and cationic charge. Also, it has been
discussed in this report several applications for the hydrogel such as (Domestic uses, Diapers,
Watering beads, Plastic surgery, Environmental applications, Bacterial culture And Drug
delivery applications) as it became more popular for its vast advantages in several industries.

References
Centre, I. I. (2007). Retrieved from www.issn.org: www.issn.org
J, K. (2002). Polymer chemistry: swell gels.Nature 417: 388-389, 391.
Jinsub, S. (1986). Hydrogels in medicine and pharmacy.
K, P. (1998). Modern superabsorbent polymer.
Khoylou F, N. (2009). Radiation synthesis of superabsorbent.
M, S. J. (2011). Hydrogels in regenerative.
Raju KM. (2001). Synthesis of novel superabsorbing.
Raju KM. (2001). Synthesis of novel superabsorbing copolymers for agriculture.
SC, L. (2013). Hydrogels for delivery of bioactive agents: a historical perspective.Adv Drug
Deliv Rev 65: 17-20.