HYDROGEL: AN

OVERVIEW
INTRODUCTION : Hydrogels are crosslinked materials
with viscoelastic properties and network structure caused
by cross-linker and the solvent, respectively.
Hydrogels are a three-dimensional network, which can be
formed by cross-linking polymer chains,which renders it
the property of crosslinking.
The cross-linking of these polymers are a result of
covalent, hydrogen bonding, van der Waals forces or
physical entanglements.
Hydrogels can hold a large amount of water, more than
400 times its original weight, up to thousands of times
their dry weight.
TYPES OF HYDROGEL:

PHG materials are classified based

on different points of view.
Classification is based on:
Environment responsive hydrogels
Preparation methods
Material resources
Morphological characteristics
Environment responsive hydrogels are
further divided into various categories:
1. Temperature sensitive Hydrogels:
Three types of temperature dependent hydrogels are found :
Negative temperature sensitive hydrogels: If temperature supplied is
less than LCST(Lower Critical Solution Temperature) then Swelling occurs
and if If temperature supplied is more than LCST(Lower Critical Solution
Temperature) then Shrinking occurs. It was observed that more the
presence of hydrophilic constituent, lower is the LCST.
Examples:PNIPAAm,PEDAAm

Positive temperature sensitive hydrogels: If temperature supplied is

more than UCST(Upper Critical Solution Temperataure) then Swelling
occurs and if If temperature supplied is less than UCST(Upper Critical
Solution Temperataure) then Shrinking occurs.
Examples:poly(AAM-co-BMA)

Thermo reversible hydrogels: They are same as negative and positive

temperature sensitive hydrogels but only differ in their
types of bonds. They are NOT covalently cross linked. They show sol-gel
phase transition instead of swelling and shrinking phenomena. It depends
on glucose concentration in the surrounding medium.
2. pH sensitive Hydrogels:
These are of two types:
Anionic: When pKa of polymer is more than the pH of
solution, Swelling occurs because of the increase in
the electrostatic repultion of the network. It contains
carboxylic and sulphonic groups.
Examples:PAA,PMAA,PEAA,PPAA,PBAA
Cationic: When pKb of polymer is more than pH of
solution, Swelling occurs because of the increase in
hydrophilicity and so does electrostatic repulsion. NH2
to NH3+ conversion takes place.
Examples: polyEthyl imine
 Other classifications based on
environmental response are:
3. Electric signal sensitive
4. Light,sound,magnetic field sensitive
5. Pressure sensitive

Classifications based on :
1. Preparation method:
Grafting
Crosslinking
Radiation
2. Material resources:
Natural
Semi synthetic
Synthetic
3. Morphological features:
Particle
Powder
Spherical
Fiber
Emulsion
 Polymerization
techniques:
Several polymerization techniques have been used to
synthesize and prepare PHG:
Solution polymerization
Aqueous polymer solution
Radiation polymerization
Photo polymerization
Suspension polymerization
Reversible addition-fragmentation chain transfer (RAFT)
polymerization
Free radical polymerization
But solution, suspension and radiation polymerization are the
three most important types of polymerization techniques.
 Solution polymerization
In solution polymerization, the ionic or neutral monomers are mixed
with the multifunctional cross-linking agent. The polymerization is
initiated thermally by UV-irradiation or by a redox initiator system. The
presence of solvent is the major advantage of the solution
polymerization over the bulk polymerization method to serve as a heat
sink.
Suspension polymerization
Suspension polymerization is used to prepare spherical PHGs or micro-
particles with a size range of 1 mm to 1 mm. The polymerization is
initiated by radicals from thermal decomposition of an initiator. The
inverse suspension technique has been widely used for preparation of
hydrogels of polyacrylamide because of its easy removal and
management of the hazardous residual acrylamide monomer from the
polymer.
Polymerization by Irradiation
Gamma rays and electron beams, has been used to initiate the
polymerization for preparing the PHGs of unsaturated compounds. It
results in the formation of radicals on the polymer chains. The major
advantage of the radiation initiation over the chemical initiation is that
the production relatively pure and initiator free.
 Methods to produce
hydrogel
1.Physical crosslinking :
Various types of physical cross linking methods are adopted, they
are:
Heating/cooling a polymer solution
Physically cross-linked gels are formed when cooling hot solutions of
gelatine or carrageenan. The gel formation is due to helix-formation,
association of the helices, and forming junction zones.

Fig : Gel formation due to aggregation of helix upon cooling a

hot solution of carrageenan.
Ionic interaction
Ionic polymers can be cross-linked by the addition of di- or tri-
valent counterions. This method underlies the principle of gelling a
polyelectrolyte solution (e.g. Na+ alginate-) witha multivalent ion
of opposite charges.
Examples : chitosan-polylysine, chitosan-glycerol phosphate salt

Fig : Ionotropic gelation by interaction between

anionic groups on alginate (COO-) with divalent
metal ions(Ca2+)
 H-bonding
H-bonded hydrogel can be obtained by lowering the pH of aqueous
solution of polymers carrying carboxyl groups.
Examples: hydrogen-bound CMC (carboxymethyl cellulose) network

Fig : Hydrogel network formation due to intermolecular H-bonding in

CMC at low pH
Other methods under physical cross linking
include :
Maturation: Here aggregation of the proteinaceous
components, induced by heat
treatment, increases the molecular weight and subsequently
produces a hydrogel form with enhanced mechanical properties
and water binding capability

Freeze thawing: Physical cross-linking of a polymer to form

its hydrogel can also be achieved by using freeze-thaw cycles.
The mechanism involves the formation of micro crystals in the
structure due to freeze-thawing.
Examples : freeze-thawed gels of polyvinyl alcohol and xanthan

Complex coacervation: Complex coacervate gels can be

formed by mixing of a polyanion with a polycation. The
underlying principle of this method is that polymers with opposite
charges stick together and form soluble and insoluble complexes
depending on the concentration and pH of the respective
2. Chemical crosslinking:
There are various chemical methods to obtain hydrogels. The
major techniques being using cross linking agents, grafting etc. A
brief description of a few chemical crosslinking methods are:

Use of chemical cross linkers: The technique mainly

involves the introduction of new molecules between the
polymeric chains to produce cross-linked chains.
Example: Hydrogel prepared by cross-linking of corn starch and
polyvinyl alcohol using glutaraldehyde as a cross-linker.

Grafting: Grafting involves the polymerization of a monomer

on the backbone of a preformed polymer. The polymer chains are
activated by the action of chemical reagents, or high energy
radiation treatment. The growth of functional monomers on
activated macro radicals leads to branching and further to cross-
linking
Two types of grafting is generally performed :
o Chemical grafting
o Radiation grafting
Fig: Grafting
3. Radiation cross-linking
Radiation cross-linking is widely used technique since it does not
involve the use of
chemical additives. Here the modification and sterilization can be
achieved in single step and hence it is a cost effective Process. This is
main of three types:

Aqueous state radiation: Here the water radiolysis generates

reactive free radicals which can interact with the polymer solute

Radiation in paste: Under these conditions the concentration of

the polymer is
high such that both direct action of the radiation can form free
radicals and also there is also sufficient water present to be radiolysed
to form OH and related radicals

Solid state radiation: The method is used for crystal lattice

modification for
semiconductors and gemstones, etc., by which the crystalline
Characterization of hydrogel
1.Solubility
Method A
Dried sample is immersed in
deionised water for 16 h or
48 h at room temperature.
The gel fraction is then
measured as follows:
gel fraction=(Wd/Wi)*100
Where, Wi is the initial
weight of dried sample and
Wd is the weight of the dried
insoluble part of sample
after extraction with water.
Method B
The weight (W1) of a 70 mm glass
fibre paper (pore size 1.2 micron) is
determined.
1-2 wt% (S) dispersion can be
prepared in distilled water followed
by overnight hydration at room
temperature.
The hydrated dispersion is then
centrifuged for 2-5 minutes at
2500 rpm prior to filtration.
Drying of the filter paper is carried
out in an oven at 105oC followed
by cooling to a constant weight
(W2).
%hydrogel=((W2-W1)/S)*100
2.Swelling
Method A Method B Method C
Dry hydrogel A volumetric Dry hydrogel is
immersed in
vial is immersed in deionised
deionised water for
used where 0.5- water for 16 hrs
48 hrs.
1 gm dry After swelling,
It is then filtered
hydrogel is hydrogel was filtered
through stainless
using 100 mesh
steel 30 mesh dispersed in stainless steel screen
screen. water(25-30ml) Swelling=(C/B)*100
Swelling= Centrifugation
(Ws-Wd)/100 C=wt of Dry hydrogel
is performed B=wt if insoluble
Ws=wt of swollen Free water is
state portion after water
removed extraction
Wd=wt of dry state
Then method
A is used to
 FTIR(Fourier Transform InfraRed
spectroscopy)
Fourier transform infrared spectroscopy
(FTIR) is a technique which is used to
obtain an infrared spectrum of absorption
or emission of a solid, liquid or gas. An FTIR
spectrometer simultaneously collects high
spectral resolution data over a wide
spectral range.
This technique is widely used to investigate
the structural arrangement in hydrogel by
comparison with the starting materials
SEM(Scanning Electron Microscopy)
The SEM is routinely used to generate high-
resolution images of shapes of objects (SEI) and to
show spatial variations in chemical compositions:
1) acquiring elemental maps or spot chemical
analyses 2)discrimination of phases based on
mean atomic number (commonly related to
relative density), and 3) compositional maps based
on differences in trace element "activitors"
(typically transition metal and Rare Earth
elements)
This is a powerful technique widely used to capture
the characteristic network structure in hydrogels
Light Scattering
Gel permeation chromatography coupled
on line to a multi angle laser light
scattering (GPC-MALLS) is a widely used
technique to determine the molecular
distribution and parameters of a polymeric
system. Hydrogel in a polymeric system
can be quantified using this technique. This
technique is widely used in quantifying the
hydrogels of several hydrocolloids such as
gum arabic, gelatine and pullulan.
Rheology
Rheology is the study of the flow of matter,
primarily in a liquid state, but also as 'soft solids'
or solids under conditions in which they respond
with plastic flow rather than deforming elastically
in response to an applied force. It applies to
substances which have a complex microstructure,
such as muds, sludges, suspensions, polymers and
other glass formers.
This technique has been used to characterize the
network structure in seroglucan/borax hydrogel,
chitosan based cationic Hydrogels and a range of
other hydrocolloids.
NMR(Nuclear Magnetic Resonance)
This used to characterize and quantify the amount of free
and bound water in hydrogels. The proton NMR gives
information about the interchange of water molecules
between the so-called free and bound states.

DSC(Differential Scanning
Calorimetry
It is also used to characterise and quantify the amount of free
and bound water in hydrogels. The use of DSC is based on the
assumption 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 hydrogel
sample being tested. The bound water is then obtained by
difference of the measured total water content of the hydrogel
test specimen, and the calculated free water content.
 Applications of hydrogel
pH sensitive hydrogels are able to convert chemical energy to
mechanical energy. Therefore they are used in artificial muscles.
Thermo sensitive PHGs have been used as drug delivery systems.
Electro sensitive PHGs have been applied in controlled drug delivery
systems.
Light sensitive PHGs are used to develop photo responsive artificial
muscles, switches and memory devices.
Used in ocular lens.
Temperature sensitive hydrogels are used in water removal processes.
Used for application of removal of heavy metals from aqueous solutions.
Control release fertilizer to reduce pollution.
Used in plant growth and production, textile, paper and pulp production
industries.
In pharmaceuticals field, PHG materials have special application
including diagnostic, therapeutic, and implantable devices such as
catheters, biosensors, dental materials artificial skin, and tissue
engineering.