Electrospun Nanofibers New Generation Ma Free Good

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Materials Science and Engineering B 217 (2017) 36–48

Contents lists available at ScienceDirect

Materials Science and Engineering B


journal homepage: www.elsevier.com/locate/mseb

Review

Electrospun nanofibers: New generation materials for advanced


applications
S. Thenmozhi a,b, N. Dharmaraj a,⇑, K. Kadirvelu b, Hak Yong Kim c
a
Inorganic & Nanomaterials Research Laboratory, Department of Chemistry, Bharathiar University, Coimbatore 641 046, India
b
DRDO-BU CLS, Bharathiar University Campus, Coimbatore 641 046, India
c
Department of Textile Engineering, Chonbuk National University, Chonju 561-756, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Electrospinning (E-spin) is a unique technique to fabricate polymeric as well as metal oxide nanofibers.
Received 6 October 2016 Research on electrospun nanofibers is a very active field in material science owing to their novel appli-
Received in revised form 10 December 2016 cations in diverse domains. The main focus of this review is to provide an insight into E-spin technique
Accepted 3 January 2017
by understanding the working principle, influencing parameters and applications of nanofibers in differ-
Available online 25 January 2017
ent walks of life. Several hundreds of papers are published on the preparation, modification and applica-
tions of nanofibers produced by E-spin technique in the areas like sensor development, decontamination,
Keywords:
energy storage, biomedical and catalysis etc. Details on the industrial scale development of E-spin tech-
Electrospinning technique
Nanofibers
nique, current scenario and future developments are also covered in this review.
Adsorbent Ó 2017 Elsevier B.V. All rights reserved.
Catalyst
Sensor
Biomedical
Energy & environment

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2. History and evolution of E-spun NFs research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Working principle, instrumentation and operational parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1. Working principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2. Instrumentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.3. Operational parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.1. Solution parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.2. Instrumental parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.3. Ambient parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4. Applications of electrospun nanofibers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.1. Biomedical applications of E-spun nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.1.1. Wound dressing material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.1.2. Scaffolds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.1.3. Drug delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2. Applications of E-spun NFs in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2.1. Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2.2. Cells and batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.3. Applications of E-spun nanofibers in defence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.3.1. Protective clothing and sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.4. Applications of E-spun nanofibers in environmental protection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.4.1. Removal of toxic wastes by NFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

⇑ Corresponding author.
E-mail address: [email protected] (N. Dharmaraj).
URL: http://ndharmaraj.wix.com/inrl (N. Dharmaraj).

http://dx.doi.org/10.1016/j.mseb.2017.01.001
0921-5107/Ó 2017 Elsevier B.V. All rights reserved.
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 37

4.5. Miscellaneous applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45


5. Laboratory to industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6. Current scenario and future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

1. Introduction ambient parameters. It is also possible to obtain fibers of different


morphology, various chemical composition and tuneable diameter
One dimensional (1-D) materials like nanotubes, nanowires, by this technique.
nanorods and nanowhiskers have gained significance due to their
potential applications in many fields such as electronics, energy 2. History and evolution of E-spun NFs research
storage cells, fuel cells, catalysis and filtering membranes. Recent
years have witnessed voluminous reports on nanofibers (NFs) of The electrospray technique started in the late 1890s was trans-
polymers, composite metals and metal oxides with multi- formed to electrospinning in the year 1900. For better understand-
functional properties. Nanofibers are always fascinating based on ing of the history behind this novel technique, we herein listed
their unique properties like high tensile strength, large surface area (Table 1) a comprehensive, year-wise development of
and porosity. Electrospun nanofibers (E-spun NFs) also possess electrospinning.
enough scope for easy surface modifications, stretchability in addi- It is worth to mention here that most of the research publica-
tion to simple and cost effective preparation. In the last two dec- tions after 2010 dealt mainly on the applications of E-spun fibers
ades, many researchers have switched over their attention from in many field using functionalised polymers, nanoparticle incorpo-
nanoparticles to nanofibers because of the prospective application rated fibers and metal oxide composite nanofibers.
of the latter class of materials.
E-spin is the only method of choice for the large scale prepara- 3. Working principle, instrumentation and operational
tion of NFs over other available methods [1]. The reasons are easy parameters
to handle, minimum consumption of solution, controllable fiber
diameter, convenient to process, cost effective, simple and repro- 3.1. Working principle
ducible in processing the fibers and has the technical advances
(scale up process). The fiber forming technology is based on the principle of
Though the origin of E-spin was traced way back to 1930, only ‘‘electrostatic attraction” of charges. The solution has its own sur-
during late 20th century noticeable advancements, growth in terms face tension inside the syringe which can be charged outside by
of instrumentation and working parameters are reported. Several applying a high voltage power supply at the tip of the needle.
hundred reports exploring the potential of E-spin technique were Oppositely charged collector is placed at some distance (10 cm)
published after the year 2000 [2] and even now it is growing very to collect the ejected fibers. During the supply of high voltage
well because of wide applications of nanofibers in various fields (10–30 kV), the solution in the syringe emerges out by overcom-
[3–11]. ing the surface tension and form a cone like structure called
The basic principle of this technique is ‘‘electrostatic interac- ‘‘Taylore cone” (drops get ejected at the tip). Taylore cone can be
tions”. In detail, the peristaltic pump pushes the solution from elongated by high charge density on the collector [25]. Fig. 1 illus-
the needle where high voltage power supply is connected. Single trates the working principle of E-spin technique.
droplet ejected at the tip of needle will be collected in a counter
electrode called collector. It could be understand that electrostatic 3.2. Instrumentation
interactions lead to fiber formation. Apart from polymeric NFs and
composites, ceramic NFs could also be prepared by changing the E-spin instrument consists of three major parts; first and fore-
parameters such as, operational condition, solution property and most influencing part is high voltage power supply, second one is

Table 1
A comprehensive account on the advancements in E-spin technique.

S. Year Nature of advancements References


no.
1 1900, 1902 Process of E-spin patented by Cooley and Morton [12]
2 1914 Jet ejection at tip of the metal capillary by John Zeleny [13]
3 1934 Patent for the invention of E-spin instrument: Fabrication of cellulose acetate using acetone as the solvent by Formhals [14]
4 1936 Patent for air-blast fibers formation from melt rather than solution by Norton [15]
5 1938, 1940 Other patents by Formhals [16–18]
6 1950–1959 Factory production of nanofibers as filter for gas mask application (only in USSR) [19]
7 1960 Jet formation study and E-spun fibers as filtration material [20]
8 1964 Formation of Taylor cone [21]
9 1971 Apparatus to spin acrylic microfibers by Baumgarten [22]
10 1995 Doshi and Reneker reported the fibers diameter decreases with increase in distance from collector to needle tip and Taylor cone [23]
11 1996–2001 Publications related to the working parameters such as, solution, ambient and instrumental parameters. [24–26]
12 2001–2005 Synthesis and characterisation of E-spun nanofibers. Different types of E-spin instrument were introduced by different researchers [27–30]
from various countries.
13 2006-till date During these period most of the papers were put forward on the applications of E-spun nanofibers as sensors, tissue engineering [31–40]
materials, protection against chemical warfare stimulants, filters, scaffolds, batteries and catalyst. Also these nanofibers found
significant application as drug delivery system in medical field.
38 S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48

Fig. 1. Diagrammatic representation for the formation of nanofibers.

Fig. 2. Images of three different electrospinning heads; series, elliptic and concen-
tric pipes. Reprinted from ref [30].

the syringe and needle assembly (collectively called as spinneret in


needleless type) and the last one is collector. Many types of E-spin
instruments are available in the market now a day. They differ only
in the type of spinneret and collector. Some instruments employ an
electrode material as spinneret while few others contain needle-
less spinneret. But, most of the instruments are of the latter type.
Generally, two major classes of instruments such as horizontal
& vertical are in practice. In horizontal type, effective force is the
charged force obtained by applied voltage and opposite attractive
force in collector which pulls the fibers. On the other hand, in case Fig. 3. SEM images and their corresponding diameter distributions of PVP–BaTiO3
of vertical type, there are two forces draws the fibers which nanofibers with (a) 8%, (b) 10% and (c) 12% PVP. Adapted from ref [41] Ó 2012
includes collector charge as well as the gravitational pull which Elsevier.

gives narrow fibers of minimum diameter.


Among many classifications of E-spin instrument, one is based like mono-axial, co-axial and multi-axial E-spin. In single nozzle
on number of nozzles such as, single nozzle and multi-nozzle E-spin, easily soluble solutions could be spun into fibers.
E-spin, another is based on the nature and number of axial units Multi-nozzle has advantage over the former one because of the

Table 2
List of category-wise factors influencing E-spin process.

Solution parameters Instrumental parameters Ambient


parameters
Nature and molecular weight of  Natural & synthetic polymer Flow rate and gauge Optimum flow – smooth Humidity
the polymer  Conductive & non-conductive polymer diameter fibers
 High M. wt – Highly viscous solution – beaded Smaller gauge diameter –
fibers thinner fibers
 Low M. wt. - low viscous solution – droplet for-
mation at the tip
Precursor and solvent Applied voltage (8–20 kV) Temperature
Surface tension, viscosity and conductivity Distance between the tip of the needle and the Atmosphere
collector (8–18 cm)
Types of collector (Drum, plate, wheel, cocoon, disc
etc)
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 39

Table 3
Various solvents and precursors used for the fabrication of ceramic NFs.

S. Nanofibers Precursor/polymer Solvent Applied voltage and diameter of References


no. produced fibers
1 GeO2 Germanium chloride/PVP DMF 20 kV and 75 nm [43]
2 NiTiO3 Nickel acetate, titanium isopropoxide/ PVP Methanol and acetic acid 12 kV and 175 nm [44]
3 SnO2 Tin chloride/PVA Water, 1-propanol and 5 kV and 100 nm.10 kV and [45,46]
isopropanol 100 nm
4 BN/TiO2 Titanium isopropoxide, boron nitride/PVP Ethanol and acetic acid 25 kV and 187–314 nm [47]
5 MgTiO3 Magnesium ethoxide and titanium isopropoxide/ 2-methoxyethanol and DMF 17 kV and 200–400 nm [48]
PVAc
6 NiO/SnO2 Nickel chloride hexahydrate and tin chloride DMF and ethanol 10 kV and 100–200 nm [49]
dehydrate/PVP
7 ZrO2 Zirconium acetate /PVAc DMF 15 kV and 200 nm [50]
8 ZnO/SnO2 Zinc nitrate and tin chloride dehydrate/PAN DMF 18 kV and 150–315 nm [51]
9 ZnO/SiO2 Zinc acetate and tetraethyl orthosilicate/PVP DMF, DMSO, HCl and ethanol 15 kV and 200 nm [52]
10 ZrO2/SnO2 Zirconyl chloride and tin chloride dehydrate/PVP DMF and ethanol 10 kV and 100–150 nm [53]

large production of fibers. Co-axial E-spin consists of two syringe ite. An increase in the concentration of polymer solution from 8 to
and single needle; both the syringes contain solutions of different 12 wt% increased the fiber diameter by 50 nm due to the viscosity
polymers/precursors those are probably immiscible and hence change of the spinning solution (Fig. 3). Similar observation on the
impossible to use mono axial E-spin instrument. Co-axial E-spin effect of solution viscosity on the size of the nanofibers was
has got much attention due to the formation of modified NFs such reported earlier [41].
as, hollow NFs, core-sheath NFs and uni-axially aligned NFs. In the case of composite nanofibers, the polymer solution is
Waclaw Tomaszewski and Marek Szadkowski investigated the mixed with the precursor solution and then fed to E-spin for the
use of multi-jet E-spin for the fabrication of NFs. They utilized fabrication. The precursor may be a metal salt solutions (or)
three types of spinning pipes’ of E-spin heads such as series, elliptic nanoparticles. They are mixed with the suitable solvent (or) poly-
and concentric (Fig. 2) and proved that the latter two facilitated the mer solution to attain the required viscosity for electrospinning.
process by using 10 or more spinning pipes [30]. During the fabrication, the solvent gets evaporated due to its travel
The other major part of E-spin is the collector. They are of many from the tip of the nozzle to the collector. For this reason, suitable
types which include drum collector, plate collector, parallel plate, solvents need to be selected for a particular precursor. Table 3
cocoon, and disc collector etc. The choice of a suitable collector gives an account on the solvent, precursor, applied voltage and
depends mainly on the nature of application associated with the diameter of the fibers formed from electrospinning with identical
fabricated nanofibers. However, drum collectors are mostly used instrumental parameters.
to get well aligned and nanosized fibers in laboratory level exper- Viscosity, surface tension and conductivity are the major inter-
iments. Aluminium foil surrounded on the drum collector acts as related solution properties that directly influence the spinability of
the conducting material which collects the fibers. the solution. Viscosity of the spinning solution is one of the critical
Instrumental parameters such as needle tip, solution volume, aspects in fiber forming technology that can be determined by
gauge diameter and modified syringe could be selected based on varying the concentration of the polymer solution [54]. Solutions
the needle type of E-spin instrument. Needleless type of E-spin is with optimum viscosity only yield the respective fibers in the
beneficial for the large scale production of nanofibers in industries. micro to nano scale diameters. On the other hand, solutions with
both very low and high viscosity led to the formation of beaded
3.3. Operational parameters fibers.
Surface tension is defined as the force exerted in the plane of
Various parameters those influence the spinning of polymer the surface per unit length [1]. During E-spin process, the applied
solution are provided in Table 2. voltage needs to be high enough to overcome the surface tension
of the spinning solution to produce nanofibers. Solvents also fluc-
3.3.1. Solution parameters tuates the surface tension to some extent. Yang and his group
Selection of a suitable polymer for electrospinning depends on reported that the different solvents exert different surface ten-
the end use of NFs. Nanotube encapsulated nanofibers of conduc- sions. They reported that by reducing the surface tension of the
tive polymers find applications in/as sensors, electrode materials solution without changing the concentration, beaded fibers could
and bio-active materials due to their ability to stimulate electrical be converted into smooth fibers [55].
charges present inside the molecules. Nanofibers of chitosan, the Conductivity of the solution plays a key role in fiber formation
natural, crystalline biopolymer were fabricated by Kumber et al., process. Ce Wang and co-workers observed that the natural poly-
[40]. They prepared chitosan NFs using the derivative of 2- mers show higher surface tension (due to its polyelectrolytic nat-
nitrobenzyl-chitosan obtained by mixing different concentration ure) under the electric field in contrast to the synthetic polymers.
of 2-nitrobenzaldehyde with chitosan. These imino-chitosan Therefore, it results in a poor fibers formation when compared to
derivatives are very good candidates for protection against bacte- synthetic one. Conductivity of the spinning solution can be
ria, fungi and yeast. increased by adding salts such as NaCl, KCl and KBr. Generally,
The molecular weight (M. wt.) of chosen polymer is an impor- increase in conductivity results in the decrease in the diameter of
tant factor that alters the characteristics of NFs. Same polymer of the fibers and thus produce thinner fibers [53].
different molecular weight produces fibers of different diameter
[41,42]. Polymers of optimal molecular weight should be selected 3.3.2. Instrumental parameters
for smooth and continuous NFs. In 2012, Sahoo and Panda reported Flow of the solution by applied pressure is called as flow rate.
the preparation and characterisation of barium titanate nanofibers Generally, lower flow rate of the solution favours the polarisation
using E-spin technique. They made a concentration dependent of the polymer solution. The increase in flow of 1 mL/min leads
study with PVP using 8–12% weight with barium titanate compos- to the formation of beaded fibers. Diameter and shape of the gauge
40 S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48

changes the fibers diameter and morphology respectively. Increase The alignment/orientation of the fibers primarily depends on
in gauge size effects the fibers of micro scale diameter meanwhile the type of collector used such as pin, plate, cross bar, rotating rods
change in the shape of gauge (sphere and elliptic) will affect the or wheels, drum, liquid bath and disk etc. Generally, nanofibers of
fibers morphology. proper orientation are fabricated using a disk collector. Younan Xia
Diameter of the E-spun fibers changes with the change in the et al., designed a home-made collector by introducing a novel gap
applied voltage. Several research groups have demonstrated that technique for aligned fibers of PVP/tetramethyl ammonium chlo-
the fiber diameter varies by changing the applied voltage [27,56– ride solution using two silicon stripes (with certain gap) as collec-
58]. Compared with other instrumental parameters of E-spin, tor [60]. In this technique, the NFs experienced two types of forces,
applied voltage has limited influence on the diameter of nanofi- one from the splitting applied voltage and the other charges on the
bers. The distance from the tip of the needle to collector gives an surface of the silicon stripes by charged electrospun NFs. They
ample opportunity for the solvent to get evaporated. Lesser the dis- reported that the denser NFs could be obtained by increasing the
tance, thicker/beaded fibers might be formed whereas more dis- collection time and reducing the gap between the Si stripes as
tance results in the discontinuous fibers. Hence, by fixing other shown in Fig. 4. Interestingly, some NFs changed their direction
thing constant, variation in the distance between tip and collector perpendicular to the edges (marked by arrows in Fig. 4d) before
will have a pronounced effect on the fibers morphology [59]. entering the Si stripes. These change in orientation further sup-
ported the two types of forces on the fibers.

3.3.3. Ambient parameters


Effect of collector temperature on the fiber characteristics is an
important aspect in electrospinning. Kim and his group [61]
studied the effect of collector temperature on the porous structure
of E-spun nanofibers. Porous nature of nonwoven mats of PLLA
dissolved in methylene chloride was significantly influenced by
temperature of the collector. By increasing the temperature to
the boiling point of the solvent used, pores were introduced on
the nanofibers by the evaporation of the solvent molecules present
on the surface of the NFs (Fig. 5a). Further increase in the temper-
ature resulted in increased pore size and more number of pores on
the fibers (Fig. 5b and c) due to an accelerated evaporation of the
solvent. A slight decrease in pore size occurred when the temper-
ature reaches 60 °C owing to the evaporation of bounded solvent
molecules with-in the viscose polymer by the acceleration of
volatility of the solvent (Fig. 5d). The porous nature disturbed
vastly by the high mobility and insufficient solidification of PLLA
by increase in temperature of the collector to the glass transition
Fig. 4. (A) Dark-field optical micrograph of PVP NFs collected on top of a gap
formed between two silicon stripes. (B and C) SEM images of same sample, showing temperature (Tg) of the polymer (Fig. 5e).
NFs deposited (B) across the gap and (C) on top of the silicon stripe. (D) SEM image Temperature and humidity are inter-related ambient parame-
of NFs region close to the edge of the gap. Reprinted with permission from ref [60] ters involved in the fiber forming technique. Increase in tempera-
copyright 2003, American Chemical society ture will decrease humidity and evaporates the solvent faster.

Fig. 5. SEM images of E-spun PLLA fibers as a function of collector temperature; (a) room temperature (21 °C), (b) 40 °C, (c) 50 °C, (d) 60 °C and (e) 70 °C.
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 41

Fig. 6. Diagrammatic illustration to high light the practical applications of E-spun NFs

High humidity will lead to thick fibers of enlarged diameter. Rabolt cles are reported to exhibit efficient antimicrobial potential for bet-
et al., reported that the increase in humidity produces porous NFs. ter curing. Recently, attention turn on nanofibers decorated with
The optimised humidity for the fabrication of polystyrene NFs was nanoparticles and their activity against micro-organisms. In
less than 25% [62]. Hence, optimum level of humidity should be 2014, the work published by Il Keun Kwon et al., has well demon-
maintained for appropriate porous NFs. strated that the silver nanoparticles containing chitosan (CS) NFs
were prepared using E-spin technique. The prepared NFs showed
4. Applications of electrospun nanofibers chelate ion between silver and amine group of chitosan. CS NFs
were tested against Pseudomonas aeruginosa (P. aeruginosa) and
E-spun nanofibers are characterised with large surface area to Methicillin-resistant Stapylococcusaureus (MRSA) which revealed
volume ratio, a beneficial property for application as scaffolds, sen- that NFs are more effective on P. aeruginosa than MRSA [63]. This
sors, filters, membranes, batteries, protective clothing, wound study demonstrated that the chitosan was inactive against the
dressing and catalyst. In the early stages, applications in biomedi- tested micro-organisms, wherein silver nanoparticles loaded chi-
cal and tissue engineering field enlightened research on nanofibers. tosan NFs exhibited significant activity by restricting the respira-
Over the years, applications were also extended to many fields tion of micro-organism due to attraction of positively charged
(Fig. 6) based on the surface and chemical properties of nanofibers. silver nanoparticles on the negatively charged cell membrane.
Table 4 lists few applications of NFs prepared by E-spin technique. Mathew group [92] also reported the formation of chitosan/PEO
nanofibers reinforced with chitin nanocrystals isolated from crab
4.1. Biomedical applications of E-spun nanofibers shells using hydrochloric acid. They prepared two different NF
mats, without chitosan (M100) as control and the other was chitin
4.1.1. Wound dressing material reinforced mats (M50ChNC50) with random and cross-linked ori-
Wound dressing is an essential step for rapid healing of the entations. They have added ‘‘genipin solution” to both M100 and
affected part and also offers protection against infection due to M50ChNC50 NFs for the preparation of cross-linked mats XM100
micro-organisms. Conventional wound dressing materials include and XM50ChNC50 respectively. SEM and AFM images of the sam-
hydrocolloids, hydrogels and alginate salts. Also, silver nanoparti- ples are shown in Fig. 7A and B, respectively. Randomly oriented,
42 S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48

Table 4
Applications of E-spun NFs in different fields.

S. Material Nature Applications References


no.
1 Chitosan-Ag nanoparticles (NPS) Nanofibers Antibacterial wound dressing material [63]
2 Silk-Ag NPs Nanofibers Antibacterial wound dressing material [64]
3 Chitin Nanofibers Improved antimicrobial activity [65]
4 Chitosan-Ag NPs-PVA Multicomponent Antimicrobial activity, Wound dressing [66]
Nanofibrous mat material
5 Polyurethane-Cellulose acetate-Zein Composite mats Wound dressing material [67]
6 Sodium alginate-Poly(ethylene oxide) Core-shell nanofibrous Tissue engineering [68]
scaffold
7 Poly(D,L-lactide-co-trimethylene carbonate) (PLMC), nano Fibrous scaffolds Bone screw hole healing [69]
hydroxyapatite (HAp)
8 Chitosan-PVA-Clotrimazole-microemulsion Nanofibers mats Oral candidiasis [70]
9 PEO-Chitosan-Graphene oxide Composite nanofibrous Drug delivery [71]
scaffolds
10 PVA-curcumin/ PVA-cyclodextrin curcumin complex Nanofibers Drug delivery [72]
11 Polyethyleneimine (PEI)-PVA –Au NPs Nanofibers Reduction catalyst [73]
12 Ni-W-carbon nanofibers Nanofibers Catalyst [74]
13 PVA/PAA-Poly(amidoamine) dendrimer stabilized Au NPs Nanofibrous mats Catalyst for Coupling Reactions [75]
14 Polyaniline-FeCl3 Nanofibers Acylation catalyst [76]
15 PEI/PVA- Pd NPs Nanofibers Reduction of chromium (VI) to (III) [77]
16 Poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP)- Nanofibers Li-ion batteries [78]
LiMn2O4 NPs – TiNb2O7
17 PVC-b-cyclodextrin- iodosobenzoic acid Nanofibers Protective wear [79]
18 PVC-MgO NPs, PVDF-MgO NPs, PSU-MgO NPs. Nanocomposite Protective clothing [33]
membrane/nanofibers
19 PVDF-MWCNT-Pt NPs Nanofibrous membrane Biosensor and catalyst [80]
20 Apoferritin-encapsulated catalytic NPS with in WO3 NFS Nanofibers Sensor [81]
21 PVP-Alumina Nanofibers Removal of toxicants [82]
22 Poly(vinylalcohol)/Tetraethyl orthosilicate/ Hybrid nanofibers Removal of Uranium (VI) [83]
Aminopropyltriethoxysilane (PVA/TEOS/APTES)
23 Ordered meso-porous silica–carbon (OMSCFs) Composite nanofibers Extraction and pre-fractionation of peptides [84]
24 Chitosan-Graphene oxide Composite nanofibrous Removal of heavy metals [85]
adsorbent
25 PAN-Activated carbon Nanofibers Removal of toxic industrial chemicals (TIC) [86]
26 PAN-Calixarene Nanofibers/membranes Adsorbent and catalyst [87]
27 Oxime-grafted PAN Nanofibers membrane Adsorption of dyes [88]
28 PAN Nanofibers Adsorption of dye [89]
29 Cellulose Nanofibers Adsorbent for ion-exchange chromatography [90]
30 PAN-Manganese activated zinc silicate Nanofibers Chromatography and detection of ultraviolet- [91]
active compound

Fig. 7. (A) SEM images of (a) M100, (b) M50ChNC50 (c) XM100 and (d) XM50ChNC50 (B) AFM images of (a) M100, (b) M50ChNC50 and (c) XM50ChNC50. Reprinted from ref
[92], copyright 2014, with permission from Elsevier.
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 43

porous, smooth fibers of simple chitosan/PEO (M100) with dis- of 4 h. The release mechanism proved that the initial burst fol-
persed nanocrystalline chitin were observed from Fig. 7A (a). How- lowed by sustained release of CZ as a result of dissolution of sur-
ever, cross linking with genipin solution altered the morphology face moieties followed by layer by layer as discussed in Higuchi’s
and porous structure of the resulting nanofiber as a function of pseudo steady state approach. These nanofibrous mats also exhib-
concentration of PEO and chitin as well as the solubility of PEO ited very good antimicrobial activity with less toxicity.
in water (Fig. 7A (c and d)). AFM images (Fig. 7B) also supported
the results of the SEM images related to the fiber morphology 4.1.3. Drug delivery
and number of pores after cross linking of M100 and M50ChNC50 In vitro studies on the delivery pattern of an antibiotic drug
NFs. An essential criterion for better wound dressing material is a loaded into nanofibrous mats was carried out by Zong et al. They
good water transmission quality. All the above four samples have produced mefoxin loaded PDLLA NFs by optimising the instrumen-
very good water holding capacity by adsorption and swelling. Par- tal parameters such as electric field, concentration, salt addition
ticularly, cross linked fibers possess more tensile strength and high and feeding rate. As-prepared NF membrane was treated in a
Young’s modulus with appropriate flexibility. Cyto-compatibility 20 mL buffer solution for in vitro drug release study. Complete
test done using cells comprising adipose derived (ASCs) stem cells release of the drug at 48 h was confirmed from the release profile
and L929 cell line demonstrated that all those mats were compat- [56].
ible with adipose derived stem cells after 7 days and hence a Recently, several new drugs are designed to cure cancer disease
potential candidate for wound dressing application. efficiently. Common cancer treatments have many limitations such
as clinical toxicity in radiotherapy, toxicity to healthy cells by over-
4.1.2. Scaffolds dose of drugs in chemotherapy and limited distribution of drugs in
Experiment to grow cells and tissues in laboratory is an intense blood vessels. In this connection, nanofibers extend its role in can-
field of research for human welfare. One of the major develop- cer therapy by easier drug carrier and release material. Shaobing
ments behind tissue engineering is the scaffold formation. The Zhouand co-workers developed a new device with core-shell nano-
polymers for scaffold materials are chosen by their hydrophobic fibers as implant material for safe and effective cancer treatment. It
and hydrophilic nature, drug adhesion and release tendency as is an excellent work in which the folate-conjucated PEG/PCL
well as the type of mat structure. High surface area and short dif- copolymer layered micelle with drug (doxorubicin) loaded nanofi-
fusion passage length of nanofibers increased their use as scaffold bers prepared by co-axial E-spin technique (Fig. 8). Core and shell
material by higher rate of drug release than the bulk material. of the nanofibers were micelle/PVA and gelatin solution respec-
Nanofibers are reported to possess control over the drug release tively. These nanofibrous mats with the micelle examined for ther-
and hence improved its efficiency towards the sustained discharge apeutic action revealed efficient killing of tumour cells, with
of drug rather than the burst release. Protein drug loaded nanofi- minimal loading of drug and reduced frequency of drug adminis-
brous scaffold prepared by Unnithan and Kim group consisted of tration and thereby improved the survival of affected people
Polyurethane (PU)/cellulose acetate (CA)/zein composite NFs mats [93]. Though many advantages are associated with core-shell
loaded with streptomycin, an antimicrobial drug [67]. Soft, model, it suffers from limitations such as barrier to cross the blood
hydrophobic and good oxygen permeable PEO was mixed with vessels, limited solubility and nonspecific uptake of the drug.
hydrophilic CA for adsorption of moisture or pus from the wound.
An antimicrobial drug was incorporated into the NFs to inhibit the 4.2. Applications of E-spun NFs in chemistry
growth of micro-organism. Then, the mat was loaded with zein
protein for better attachment and proliferation of cells with good 4.2.1. Catalyst
blood clotting ability. These composite NFs showed efficient anti- Ramakrishna et al., published a review article in 2012 on the E-
bacterial activity, blood clotting and platelet activation ability. spun composite NFs and their multifaceted applications in various
Blood clotting and platelet activation study was done by optical fields such as energy, filter membranes, smart materials, sensors
density measurement. Cell attachment study was conducted using and biotechnology [39]. E-spun nanofibers proved to be an excel-
3T3-L1 fibroblast cell and quantified by MTT assay. Composite lent material as catalyst for organic transformations. Among the
fibers allowed the growth of cells inside the nanofibers where as several hundreds of reports compiled with nanofibers, significant
it was on the surface in neat PU fibers. Presence of hydrophilic zein numbers of them related to their applications as catalysts are
protein improves the cell attachment and cellulose acetate explained below. Nanofibers of poly(ethyleneimine)/poly(vinylalco
enhances the cell growth. Drug compound inhibits the growth of hol) (PEI/PVA) immobilized with gold nanoparticles were prepared
Escherichia coli K12-MG1655, Salmonella typhimurium, Vibrio vul- and utilized as a catalyst for reduction reaction [73]. It was found
nificus CMCP6, Staphylococcus aureus ATCC25923 and Bacillus sub- that Au NPs of 11.8 nm size immobilized on PEI/PVA NFs of
tilis by the addition of Streptomycin drug on the NFs. 490 nm displayed excellent catalytic activity and re-usability for
Commercially formulated candidiasis of lozenges, mouthwash, the transformation of 4-nitrophenol to 4-aminophenol.
oral gels and suspensions exhibited initial burst and rapid decline Hiroyoshi Kawakami and group successfully prepared a position
to sub-therapeutic concentrations. To achieve the sustained release controlled porphyrin moieties on E-spun NFs by controlling the
of the drug as well as better therapeutic usage, micro-adhesive electrospinning parameters and considering the characteristics of
properties are needed for the scaffolds. Recently, a novel scaffold porphyrin moieties [94]. They prepared three different samples
for oral candidiasis application was reported by Praneet Opanaso- of NFs using 5,10,15,20-tetrakisphenyl-21-H,23-H-porphyrin(TP
pit and his group in the year 2015 using E-spin technique [70]. P),5,10,15,20-tetrakis(N-methyl-4-yridyl)-21,23-H-porphyrin
Micro-emulsion was prepared by mixing oleic acid, Tween 80 (TMPyP) and 5,10,15,20-tetrakis(N-methyl-4-pyridyl)-porphyrin-
and co-surfactants like, benzyl alcohol (BzOH), ethyl alcohol, and manganese(III) chloride (Mn-TMPyP). In this study, the authors
isopropyl alcohol. Then, clotrimazole (CZ) was loaded on micro made a new kind of claim that the repulsion among cationic por-
emulsion and fabricated using chitosan/PVA polymer composite. phyrin molecules during E-spin process led to their arrangement
The fibrous mat showed very good CZ entrapment efficiency of at specific positions on the nanofibers. One of the types of NFs,
approximately 72.58–98.10%. Drug entrapment and delivery stud- Mn-TMPyP tested for anti-oxidant property by ‘‘Cytochrome C”
ies conducted for nanofibrous mat. The drug delivery rate could be method revealed a new way of radical scavengers for oxidative
altered by applying different formulation of micro emulsion. The stress therapies. Cellulose nanofibers functionalised with different
extent of drug release was found to be 64.81–74.15% after a period anions were prepared and properly decorated with noble metal
44 S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48

Fig. 8. Folate-conjucated PEG/PCL copolymer layered micelle (doxorubicin drug loaded) nanofibers prepared by co-axial E-spin technique. Adapted with permission from ref
[93], Ó 2015 American Chemical Society.

nanoparticles (Ru & Au) by Karvembu and his group [95]. They
applied this nanoparticles decorated NFs to understand the cat-
alytic behaviour towards the aerobic oxidation of benzyl alcohol
and aza-Micheal reaction. Surprisingly, they got 100% selectivity
with good yield (89% & 99%) in both type of reactions. Proposed
mechanism clearly explains the catalytic efficiency of Ru and Au
nanoparticles decorated on the cellulose acetate nanofibers. They
have checked the reusability and heterogeneity of the catalytic sys-
tem which reveals that catalyst could be reused efficiently up to
three times.

4.2.2. Cells and batteries


Seeram Ramakrishna and Shrinivsan Madhavi reported a novel
TiNb2O7 nanofibrous material (Fig. 10) as anode material for fuel
Fig. 9. TEM images of Au/Amide-Cal[8]/PAN nanofibers. Reprinted with permission cell application [78]. Both electrode and electrolyte material com-
from ref [87] copyright 2013, American Chemical Society. prise of E-spun nanofibers and constructed excellent Li-ion battery.
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 45

membrane performs good electro-sensing activity towards H2O2


and glucose. The prepared biosensor based hybrid nanofibrous
membrane shows linear range, lower detection limit, high selectiv-
ity, and long-term stability. Moreover, these hybrid nanofibers
were excellent catalytic material in ORR electro-catalysis. Several
factors, such as the uniform dispersion of Pt NPs, axial orientation
of CNTs, and improved b-phase of PVDF, are the main reasons for
promoting the electrochemical and electro-catalytic properties of
the E-spun PVDF-MWCNT-Pt-NP nanofibrous membrane.

4.4. Applications of E-spun nanofibers in environmental protection

4.4.1. Removal of toxic wastes by NFs


Surface functionalised E-spun NFs with active groups are
responsible for the removal of toxicants in waste water and drink-
Fig. 10. Schematic representation of Li-ion battery comprising a one-dimensional ing water by adsorption of such toxicants on their surface. NFs
component. Adapted with permission from ref [78] Ó 2014, American Chemical exhibit different adsorption behaviour based on the nature of
Society functional group on their surface. Removal of chromium (VI) and
fluoride ions using alumina/PVP NFs was reported by Hota and
co-workers. The study revealed that the maximum removal of
Newly fabricated device has delivered the reversible capacity of
chromium (VI) and fluoride was observed at pH 5 and 7 and the
116 mAh g 1 at current density of 150 mA g 1 for the applied
adsorption capacity was 6.8 and 1.2 mg/g respectively during con-
potential of 2.4 V and 278 Wh kg 1. Depends on the solid nature
tact time of 1 h according to Freundlich isotherm model and
of conductive polymeric materials, the ionic mobility was
heterogeneous adsorption process [82].
enhanced/declined and hence influence the charge/discharge
In the year 2014, Guowang Diao prepared PAN NFs membrane
capacity as well as the storage capacity. Recently, the same group
functionalised with three types of calix[8]arenes (Cal[8]),
published a feature article on E-spun NFs for constructing high per-
Ester-cal[8], Amide-cal[8] and Au immobilized on PAN-Cal[8]
formance Li-ion batteries. They elaborated about the high voltage
(Fig. 9) and studied the adsorption behaviour on the neutral red
cathode and low voltage insertion anodes with high capacity com-
and congo red dyes on them. The adsorption of congo red dyes
binations and studied in 1D configuration.
follows pseudo-second order kinetic and the rate constant was
E-spun Cu/Sn/C composite NFs were synthesised by Kim and
1.1  10 3 g mg 1 min 1. Au/Amide-cal[8]/PAN composite NFs
Kim using dual nozzle E-spin method followed by carbonization
showed excellent catalytic activity, high stability and reusability.
[96]. These composite NFs were tested for the capacity of both
Hence, Amide-cal[8] functionalised NFs act as both adsorbent for
Li-ion and Na-ion. Stable reversible performance reveals that the
dyes and catalyst to immobilise Au nanoparticles on the mem-
capacities of 490 and 220 mAhg 1 for Li-ion (600 cycle) and Na-
brane [87].
ion (200 cycles) respectively.
Oxime grafted poly(acrylonitrile) (Ox-g-PAN) NFs were pre-
pared by Haider et al., (2014) using E-spin technique [88]. They
4.3. Applications of E-spun nanofibers in defence have studied the adsorption kinetics of Ox-g-PAN on three differ-
ent dyes namely, methylene blue (MB), rhodamine B (RB), and
4.3.1. Protective clothing and sensors safranin T (ST). The order of adsorption capacity was found to be
Nanofibers with surface pores are used as catalyst for the degra- MB (102.15 mg/g) < ST (118.34 mg/g) < RB (221.24 mg/g). Efficient
dation of organic compound such as dyes, pesticides and chemical adsorption of RB was noticed than the other two dyes. The
warfare stimulants (CWS). Ramakrishna and co-workers published adsorption follows well with Freundlich isotherm model than with
a set of papers for the degradation of CWS using b-cyclodextrin (b- the Langmuir isotherm model. Patel and Hota synthesised the PAN
CD) and magnesium oxide (MgO) nanofibers with different com- nanofibers and functionalised with carboxylate anion. As-prepared
posites. In MgO/polymer composite nanofibers, reactivity order of NFs were applied for the removal of cationic dye, malachite green
the polymer composites are found to be PVC- (MG). This removal follows Langmuir adsorption isotherm and
MgO < PVDF < PSU < PVDF-MgO < PSU-MgO. They compared the pseudo-second order kinetic model. The adsorption capacity of
effectiveness of nanoparticles, charcoal and nanocomposite mem- 99% of MG dye was completed within 30 min of contact time
branes on hydrolysis of paraoxon (CWS). The fabricated composite [89]. The adsorption capacity was found to be 1038 mg/g. They
membrane (containing 5% MgO) was treated against chemical war- have also carried out the effect of pH and concentration on the
fare agent stimulant, paraoxon, and found to be about 2 times kinetic model. One more credential study on thermodynamic
more reactive than the charcoal [79]. Preparation of b-CD deriva- model reveals that the process was endothermic and spontaneous
tives by same group using E-spin shows 11.5 times faster hydroly- in nature. E-spun nanofibers act as the sorbent materials for the
sis ability than the conventional activated carbon used in removal of oestrogen from aqueous solution.
protective clothing and canisters. Moreover, [(3-carboxy-4-iodoso
benzyl)oxy-b-CD] derivative of b-CD was more efficient and faster 4.5. Miscellaneous applications
in hydrolysis of CWS than the parent b-CD or iodosobenzoic acid or
combination of both [33]. A very recent, innovative study on the application of NFs in the
A novel b-phase PVDF nanofibrous membrane decorated with field of agriculture to protect seeds against the attack from the pest
multi-walled carbon nanotubes (MWCNTs) and platinum nanopar- as well as early germination has opened up a new area of research
ticles (Pt NPs) was fabricated by an improved E-spin technique by involving this class of materials. Sheeja Rajiv group [97] utilized
Gang Wei and Zhiqiang Su [80]. These nanofibers on glass carbon cobalt nanoparticles (Co NPs) incorporated PVP/urea E-spun NFs
electrode were applied as a potential material for H2O2 and glucose as novel protecting material for one of the leguminous plant’s
bio-sensor and oxygen reduction reaction (ORR) catalyst. Electro- (cowpea) seed. They proposed that the coating of NFs on the seed
chemical data indicated that the PVDF-MWCNT-Pt-NP nanofibrous resulted in the protection from the microbes (PVP layer), much
46 S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48

Number of Papers Published on ApplicaƟons of E-spin NFs Table 5


Details of commercialised E-spin technique.

250 S. Year Company name References


no.

200 1 1980-sub micron fibers Donaldson Co., [100]


Number of papers

Inc.
2 1989-micro denier fibers DuPont [101]
150
3 1995-E-spin of nanofibers Reneker [23]
4 2008-Multinozzle electrospinning Finetex [102]
100 5 2009-Nozzle conjucate melt Teijin Fibers Ltd [103]
spinning
50 6 2011-Nozzle centrifugal spinning Fibe Rio Tech [104]
7 2012-Nozzless electrospinning Elmarco [105]

0
Biomedical
Defense Though the E-spun NFs have unique applications, still they
Environmental encounter some challenges in the production stage: (i) large vol-
Catalyst
protecƟon
ume processing (ii) reproducibility and (iii) safety. Some compa-
Fig. 11. PubMed results of ‘‘applications of electrospun nanofibers”. nies have contributed their efforts on it and constructed
equipment which could overcome these issues [101–105]. To
reduce the heavy power consumption during E-spinning and make
nitrogen fixation (urea) and abundant micro-nutrient (Co NPs). The it compatible, a battery operated handy E-spin instrument with
dissolution and release of PVP/urea/Co NPs was reported that the small volume (10.5  5  3 cm3) and light weight (about 120 g)
initial burst of PVP and then slow release of urea and cobalt was developed and tested in the laboratory level, recently [106].
enhances the germination and growth of the seed. By this method,
seeds of rare species could be stored for the long time and used at
appropriate time. Hence, this strategy will have much scope in 6. Current scenario and future work
future to explore a green revolution in agricultural sector.
To highlight the significance of E-spun nanofibers, a compara- Electrospinning is a promising technology to produce submi-
tive study on their applications was made with the help of ‘‘Pub- cron size fibers i.e., NFs from the laboratory level to industrial level.
Med” search engine and furnished in Fig. 11. The key words used Several hundreds of papers reported the preparation, characteriza-
for the search is ‘‘applications of electrospun nanofibers as wound tion and applications of NFs. Generally, nanomaterials possess
dressing, scaffold & drug delivery (collectively written as Biomed- large surface area, which is considered as an advantage for applica-
ical), sensors & protective clothing (mentioned as defence), solar tions in many fields. Particularly, electrospun nanofibers received
cell, batteries & adsorbent (denoted as environmental protection) special attention in biomedical field due to their biocompatibility,
and catalyst” as well as filters applied are journal article and adhesiveness and sterile nature. Applications are also extended to
5 years. areas like, filters, protective clothing, membranes, sensors, energy
storage devices and catalysis.
Currently, NFs are considered as suitable candidates in wound
5. Laboratory to industry dressing materials, scaffold materials, drug delivery systems, filtra-
tion membranes, catalyst for reduction, oxidation and coupling
In industries, large scale production of fibers is carried out reactions. Recently, few companies put forward their work on sup-
mainly by three types of spinning technologies. Melt spinning, ply of nanofibers for medical appliances. Batteries and fuel cells
solution spinning and emulsion spinning. Large scale production also utilize NFs as new material with enhanced energy storage
prefers melt spinning for the beneficial of environment (i.e., solvent capacity.
free method). Solution spinning requires suitable solvent to dis- Though vast majority of applications are reported already in
solve the precursor for fabrication. Emulsion spinning prefers poly- bio-medical, sensors and photo-catalytic field, still focus should
mers of high melting point [98]. be given in renewable energy storage devices and as catalysts
Laboratory level E-spin was carried out with syringe and needle (Fig. 11) for the synthesis of organic compounds, pharmaceuticals
type. However, manufacturing requires large volume of solution and fine chemicals. As of now, general preparatory methods for
for spinning. Needleless type of spinning consists of spinneret pharmaceuticals involve multiple steps under specialized reaction
(the set up includes syringe and needle) which could transform conditions. Hence, we believe that the electrospun nanofibers
large volume of solution into fibers. The scientific challenges asso- could be utilized as potential heterogeneous catalysts for organic
ciated with large scale production are clogging of the solution in reactions that might simplify the experimental protocol with com-
the holes of the nozzle, influence of electrical charge on the con- plete conversion of substrates to desired products as well as with
ductive nanofibers and inter-jet perturbation in needless spinneret low catalyst loading.
[99].
In 1934, Formhals filed his first patent for the invention of E-
spin instrument which was not much rewarded during that period, 7. Conclusion
due to the lack of characterisation techniques for the nanoscale
materials. After few decades, the development of imaging tech- Electrospinning is a simple and cost effective but fascinating
nique like SEM, TEM, AFM and STM revealed that E-spin is a won- fiber forming technology with less time consumption under opti-
derful technology for the preparation of nanofibers. It is evident mized conditions. This review article is the compilation of most
that studies on E-spun NFs are increasing continually due to their relevant information about the fundamental aspects of E-spin such
potential applications in various fields. Nowadays commercial E- as working principle, factors influencing the fiber formation and
spin equipment, accessories and E-spun fibers are available in proposed practical applications of NFs. Applications of E-spun
the market. List of companies those commercialised E-spin instru- NFs in biomedical, defence, environmental remediation and mate-
ment are given in Table 5. rial chemistry are presented. Particularly, use of E-spun NFs as
S. Thenmozhi et al. / Materials Science and Engineering B 217 (2017) 36–48 47

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4412.
regenerative purpose (both tissue and organ), filters, protective
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