Assignment # 3

Hydrogels as Fibrous Material and it application

Submitted to: Dr. Atif Islam

Submitted by: Wasif Razzaq(PhD.14.15)

Department of Polymer Engineering and Technology

University of Punjab

Electrospinning
Unlike conventional fiber spinning techniques (wet spinning, dry spinning, melt spinning, gel
spinning), which are capable of producing polymer fibers with diameters down to the micrometer
range, electrostatic spinning, or electrospinning is a process capable of producing polymer
fibers in the nanometer diameter range. Electrospinning is a novel and efficient fabrication
process that can be utilised to assemble fibrous polymer mats composed of fiber diameters
ranging from several microns down to fibers with diameter lower than 100 nm.This electrostatic
processing method uses a high-voltage electric field to form solid fibers from a polymeric fluid
stream (solution or melt) delivered through a millimeter-scale nozzle. Nanofibers are the ultrafine solid fibers notable for their very small diameters (lower than 100 nm), their large surface
area per unit mass and small pore size.
Due to the inherent properties of the electrospinning process, which can control the deposition of
polymer fibers onto a target substrate, nanofibers with complex, and seamless three-dimensional
shapes could be formed. Construction of nanoscale composite fibers by electros-inning from a
mixture of rigid rod polymers and flexible polymers is also feasible. The electrospun nanofibers
can even be aligned to construct unique functional nanostructures such as nanotubes and
nanowires. Furthermore, depending on the specific polymer being used, a wide range of fabric
properties such as strength, weight and porosity, surface functionality etc. can be achieved. This
novel fiber spinning technique provides as well the capacity to lace together a variety of types of
polymers, fibers, and particles to produce ultrathin layers. Small insoluble particles can be added
to the polymer solution and encapsulated in the dry nanofibers. Soluble drugs or bacterial agents
can be added and electrospun into nonwoven mats.
Although the process of electrospinning has been known for almost 70 years and the first patent
was issued to Formhals in 1934 (US Patent, 1-975-504), polymeric nanofibers produced by
electrospinning have become a topic of great interest for the past few years. Reneker and Chun,
who revived interest in this technology in the early 1990s, has shown the possibility to
electrospin a wide range of polymer solutions in 1996. Larrondo and Manley had performed a
similar work on polymer melts in 1981. Typically, electrospinning is applicable to a wide range

of polymers like those used in conventional spinning, i.e. polyolefine, polyamides, polyester,
aramide, acrylic as well as bio-polymers like proteins, DNA, polypeptides, or others like electric
conducting and photonic polymers. The high specific surface area and small pore size of
electrospun nanofibers make them interesting candidates for a wide variety of applications. For
instance nanofibers with a diameter of 100 nm have a ratio of geometrical surface area to mass of
approximately 100 m.
Another interesting aspect of using electrospun fibers is that the fibers may dissipate or retain the
electrostatic charges depending on the electrical properties of the polymer. The charge scan be
manipulated as well by electrical fields and the electrical polarity of the fibers is affected by the
polarity of the applied voltage. Nanofibers provide also a connection between the nanoscale
world and the macroscale world, since the diameters are in the nanometer range and the lengths
are kilometres. Therefore, current emphasis of research is to exploit such properties and focus on
determining appropriate conditions for electrospinning various polymers and biopolymers for
eventual applications including multifunctional membranes, biomedical structural elements
(scaffolding used in tissue engineering, wound dressing, drug delivery, artificial organs, vascular
grafts), protective shields in specialty fabrics, filter media for submicron particles in separation
industry, composite reinforcement, and structures for nano-electronic machines among others.

The electrospinning process

The electrospinning process uses high voltage to create an electric field between a droplet of
polymer solution at the tip of a needle and a collector plate (see Figure 1&2). One electrode of
the voltage source is placed into the solution and the other is connected to the collector. This
creates an electrostatic force. As the voltage is increased, the electric field intensifies causing a
force to build up on the pendant drop of polymer solution at the tip of the needle. This force acts
in a direction opposing the surface tension of the drop. The increasing electrostatic force causes
the drop to elongate forming a conical shape known as a Taylor cone. When the electrostatic
force overcomes the surface tension of the drop, a charged, continuous jet of solution is ejected
from the cone. The jet of solution accelerates towards the collector, whipping and bending
wildly. As the solution moves away from the needle and toward the collector, the jet rapidly thins
and dries as the solvent evaporates. On the surface of the grounded collector, a nonwoven mat of

randomly oriented solid nanofibers is deposited. Some important applications for these
nanofibers include, but are not limited to, catalytic substrates, photonics, filtration, protective
clothing, cell scaffolding, drug delivery and wound healing. Different applications may require
the fibers to possess different properties. For instance, one application might require the
nanofibers to be hydrophobic or hydrophilic; another may need the fiber to be biodegradable or
biocompatible. It will, therefore, be extremely important to completely understand the process by
which these fibers are produced.

Hydrogels as fibrous materials

Nanofibers The study of nanofibers has become extensive during the past decade due to their
unique properties, such as very high surface to weight ratio, and superior mechanical properties
compared with the bulk material. The great strength of nanofibers derives from highly aligned
molecular chains in the structure and a low probability of surface defects, which minimizes the
development of cracks. Therefore, they are used within bioengineering for drug delivery, wound
dressing, and tissue engineering applications. The interest in the latter is due to the similarity in
morphology between a mesh of nanofibers and the collagen fibers that exist in the ECM of many
tissues. Although microfibers can provide greater strength, it is preferable to use nanofibers
rather than microfibers for tissue engineering purposes; it has been reported that, because as fiber

diameter decreases biocompatibility increases, a larger surface area is beneficial for cell
attachment.
New fabrication techniques are being rapidly developed that allow a range of materials to be
formed into nanofi- bers, particularly for tissue engineering. The most commonly used technique
is electrospinning because of its simplicity, low cost, and suitability for natural and synthetic
polymers, ceramics, and metals. The process works by drawing material from a blunted syringe
needle using a high voltage towards an earthed collecting plate, upon which a nonwoven mesh of
fibers is formed; the mesh can be either random or aligned fibers depending upon the type of
collector used. The resulting fiber diameters range from a few nanometers to several
micrometers. There are many variations of electrospinning, including using multiple needles, no
needle, bubble electrospinning, and electro-blowing, all of which can produce fibers less than 1
mm in diameter.
Other methods capable of producing nanofibers include wet spinning, centrifugal spinning,
microfluidic spinning, melt blowing, phase-separation, and drawing, although typically these
produce fibers at the microscale. Coaxial electrospinning is also commonly used for tissue
engineering because the fibers can combine a strong synthetic polymer core surrounded by a
sheath of a natural polymer, such as gelatin, to improve cellfiber interactions. The mechanical
properties of nanofibrous meshes depend on the material properties of the individual fibers, fiber
diameter, mesh porosity, fiber alignment, and bonding between fibers. Some researchers have
attempted to model how individual fibers affect the mechanical properties of an electrospun
mesh, butthis is yetto be fully understood. The stiffness of individual electrospun fibers has been
shown to increase with decreasing fiber diameter; however, this does not correlate with
increasing the stiffness for the overall electrospun mesh. There are multiple studies on how the
solution properties, such as altering the polymer used or the polymer concentration, affect the
mechanical strength of the overall mesh; however, only a few have assessed how the mesh
morphology affects the mechanical strength. It has been shown that the tensile strength of the
mesh can both increase or decrease with a decrease in fiber diameter, suggesting the overall
physical properties of the mesh are affected by other factors, such as pore size or the interaction
between fibers. It has been theorized that, for electrospun meshes, it is not only fiber or mesh

morphology that affects the mechanical properties, but also the conditions that were used to form
the meshes.

Hydrogels fibers in tissue engineering

The field of tissue engineering has developed to meet the tremendous need for
organs and tissues. In the most general sense, tissue engineering seeks to
fabricate, living replacement parts for the body. The necessity of tissue engineering
is illustrated by the ever-widening supply and demand mismatch of organs and
tissues for transplantation. This trend persists, as demonstrated by the fact that
only 23,407 people received transplants from July 2000 to July 2001, while 79,902
people awaited them. Numerous strategies currently used to engineer tissues
depend on employing a material scaffold. These scaffolds serve as a synthetic
extracellular matrix (ECM) to organize cells into a three-dimensional architecture
and to present stimuli, which direct the growth and formation of a desired tissue.
Depending on the tissue of interest and the specific application, the required
scaffold material and its properties will be quite different. Common scaffold
materials include poly(lactide-co-glycolide) (PLG). PLG are hydrolytically degradable
polymers that are FDA approved for use in the body and mechanically strong.
However, they are hydrophobic and typically processed under relatively severe
conditions, which makes factor incorporation and entrapment of viable cells
potentially a challenge. As an alternative, a variety of hydrogels, a class of highly
hydrated polymer materials (water content X30% by weight, are being employed as
scaffold materials. They are composed of hydrophilic polymer chains, which are
either synthetic or natural in origin. The structural integrity of hydrogels depends on
crosslinks formed between polymer chains via various chemical bonds and physical
interactions. Hydrogels used in these applications are typically degradable, can be
processed under relatively mild conditions, have mechanical and structural
properties similar to many tissues and the ECM, and can be delivered in a minimally
invasive manner.

Hydrogels fibers in drug delivery

Drug delivery systems (DDSs) are regarded as a promising means to control postoperative inflammation, although design improvements are needed to increase
biocompatibility and effectiveness, as well to prolong controlled release of the drug.
Interest in biodegradable polymers, and specifically in a DDS matrix, has been
growing. The main reason for this is that delivery systems based on biodegradable
polymers do not require removal of the polymers from the body at the end of the
treatment period, as they degrade into physiologically occurring compounds that
can be readily excreted from the body. This capability has several merits, including
a reduction in stress to the body resulting from the need not to physically remove
the delivery system and a reduction in cost with a reduction in time spent by the
end-user. Among the various available biodegradable polymers poly(vinyl alcohol)
(PVA) has unique properties, including a hydrophilic character, allowing it to absorb
water and swell easily. PVA has been used in various modern technologies, such as
hydrogels, polyelectrolytes, optical applications and biomaterials, including soft
contact lenses, implants and artificial organs. This wide variety of applications is
possible

due

to

their

inherent

non-toxicity,

non-carcinogenicity,

high

biocompatibility and high degree of swelling in aqueous solutions. Because of these

advantages, much attention has been focused on electrospinning PVA for
applications in different fields, such as biosensors, antimicrobial fibers, composites,
macroporous and nanoporous films and membranes and filtration applications.
Despite these advantages, the main barrier to the use of PVA hydrogel is that it
results in an initial burst of drug release in the body due to its excellent swelling
properties. Therefore, it is difficult to obtain a stable long-term effect. Eventually it
will be necessary to develop a DDS technology which can control the release period
and rate effectively. In our study the effect of fluorination on electrospun hydrogel
fibers was investigated for an effect on controlled drug release, in order to solve the
above problems of PVA, using two technical methods. The first involves control of
the diameter of the PVA fibers by exploiting the advantages of nanotechnology. The
second uses a direct fluorination method which is very simple, efficient and
economical and requires a very short time to implement.