3

Processing of composite functional nanofibers

Y. CAI, Q. WEI and F. HUANG,
Jiangnan University, China

Abstract: This chapter introduces the formation mechanisms and

potential applications of composite nanofibers, including coverage of
polymer/polymer composite nanofibers, polymer/nanoparticles composite
nanofibers and polymer/inorganic salts composite nanofibers. The
methods and principles of electrospinning and future trends of composite
nanofibers are also explored. The potential uses for the different
nanofibers are identified; many of these are still in the development stage,
but some are already fulfilling roles in medicine, industry etc.

Key words: electrospinning, composite nanofibers, application.

3.1 Introduction
Nanofibers have attracted a great deal of attention due to their remark-
able properties. Compared to conventional fibrous structures, nanofibers
are lightweight with small diameters, controllable pore structures and high
surface-to-volume ratio, making them ideal for use in applications as var-
ied as filtration, sensors, protective clothing, tissue engineering, functional
materials and energy storage.1–5 However, the development of new compos-
ite nanofibers holds even greater potential and investigation of new poly-
mer composite nanofibers aimed at further developing their multifunctional
possibilities and enhancing both their physical and chemical properties has
gained extensive interest. Polymer composite nanofibers generally consist of
two or more composites, with a range that includes polymer/polymer com-
posite nanofibers, polymer/nanoparticle composite nanofibers and polymer/
inorganic salts composite nanofibers, among others.

3.2 Formation of polymer and polymer composite

nanofibers
Polymer/polymer composite nanofibers are defined as nanofibers com-
posed of two or more polymers. Polymer/polymer composite nanofibers
can be produced using two experimental methods. The first method is a
one-step electrospinning procedure. Direct electrospinning of polymer

38

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 Processing of composite functional nanofibers 39

solutions, containing two kinds of polymers dissolved in homogeneous or

mixed solvents, leads to the formation of composite nanofibers. Fabrication
of nanofibers from biopolymers is attracting increasing interest due to
the fact that biopolymers may have superior biocompatibility and biode-
gradability, are generally nontoxic, renewable and available at low costs,
and may have additional properties such as being antioxidant, antimi-
crobial or effective in relation to enzymes.6 Researchers have focused on
electrospun blends of Chitosan with other compatible polymers such as
poly(vinyl alcohol) (PVA) 7–10 and polyethylene oxide (PEO) 11–14 among
others.15 In blends, the fiber-forming ability of the cospinning agent is uti-
lized to facilitate polymer entanglement and generation of a polymer jet.
Electrospinning of polymer blends is also an efficient way to create com-
posite nanofibers that have improved material properties, such as higher
tensile strength.
The second method used in the production of polymer/polymer composite
nanofibers is co-electrospinning or coaxial electrospinning. In this process,
two kinds of polymers are dissolved in two different solvents, before being
co-electrospun with the same collector. The prepared composite nanofi-
bers may be formed with different structures, producing both hybrid struc-
ture nanofibers and core-shell structure nanofibers. The schematic views
of the co-electrospinning and coaxial electrospinning setups are shown
respectively in Fig. 3.116 and Fig. 3.2.17 The coaxial electrospinning process
is reported to be an effective and versatile process for the fabrication of
core-shell structures. Using this technique, the functional component can
be encapsulated as the core, or coated as the shell. Composites such as fer-
ritin nanoparticles/poly(2-acrylamido-2-methyl-1-propanesulfonicacid),18
poly-(N-isopropylacrylamide)/poly(methylmethacrylate),19 polycarbonate/
poly(methyl methacrylate)20 and chitosan/poly(ethylene oxide)21 have all
been electrospun for specific applications.

Roller

Pressure PVA solution PLLA solution Pressure

+ High-voltage – – High-voltage +
power power

3.1 Setup of co-electrospinning.

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40 Functional nanofibers and their applications

Core solution

Shell solution

Co-axial Taylor cone Co-axial capillary

Core
High-voltage supply
Whipping co-axial jet
Shell

Grounded
collector

3.2 Schematic of co-axial electrospinning set-up.

3.3 Formation of polymer and nanoparticle

composite nanofibers
The so-called polymer/nanoparticle composite nanofibers, consisting of
nanoscale inorganic fillers and a polymer matrix, encompass the advan-
tages of both composites. The light weight, flexibility and good moldability
of the polymer materials is combined with the high strength, heat stability
and chemical resistance of the inorganic materials.22–23 As a result, these
composite nanofibers have enhanced mechanical, electrical, optical, ther-
mal and magnetic properties, with no degradation of their transparency,
making them excellent candidates for many multifunctional applications
including membranes, biomedical devices and energy conversion and
storage systems.23–25 Polymer/nanoparticle composite nanofibers can be
obtained using several experimental methods.23 The first method is known
as the polymer template procedure, in which polymer nanofibers produced
by electrospinning or other means, are immersed into a nanoparticulate
containing composite solution to adsorb nanoparticles on the fiber sur-
face. A thermal or chemical treatment step is often introduced in addition
to obtain good particle–fiber adhesion.26 The second method used in the
formation of polymer composite nanofibers is a one-step electrospinning
procedure, in which nanofibers are produced by the direct electrospinning
of a polymer solution containing nanoparticles.27 Comparing these two
methods, the one-step electrospinning process is relatively simple and has
the advantage of producing composite nanofibers at high speed and low
cost. Use of the one-step electrospinning method facilitates the production

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 Processing of composite functional nanofibers 41

of polymer/inorganic composite ultra-thin nanofibers, which combine the

advantages of organic–inorganic hybrids with the large surface area of
nanofibers and therefore meet the needs of new materials.28 In addition,
alternative production methods including sol-gel, sputter coating and elec-
troless deposition are also frequently used.
Among various polymer/inorganic composite nanofibers, the most fre-
quently used nanoparticles included montmorillonite,1, 29–36 silver (Ag),37–38
titanium dioxide (TiO2),39–41 silica (SiO2),42–44 magnetite (Fe3O4),45 silicon
nitride (Si3N4),46 layered double hydroxides (LDHs),47 zinc oxide (ZnO),48
copper (Cu),49 β-tricalciumphosphate (β-TCP)50 and multiwalled carbon
nanotubes.51

3.3.1 Two-step electrospinning method

For this method, the polymer/nanoparticle nanocomposites are initially pre-
pared by melt blending using a twin screw extruder,29–31, 46, 50 in situ emulsion
polymerization32 and in situ polymerization.51 The composite nanofibers are
then prepared using electrospinning once the polymer/nanoparticle nano-
composites have been dissolved in a solvent. The nanoparticles most com-
monly used in this process include layer silicate clays,29–31 Si3N4,46 β-TCP50
and multiwalled carbon nanotubes.51

3.3.2 One-step electrospinning method

A simple one-step composite technique may also be used to prepare com-
posite nanofibers. The nanoparticles are initially dispersed in a solvent, as is
the polymer which may be dissolved in the same or an alternative solvent.
The two are then compounded, before the composite solution is sonicated
and electrospun to form polymer/nanoparticle composite nanofibers. The
silicate clays,33–36 TiO2,39 SiO2,42–44 Fe3O445 and LDHs47 are most commonly
used in this method. The schematic views of the electrospinning setup are
shown in Fig. 3.3.52

3.3.3 Sol-gel method

Sol-gel technology offers many possibilities for the introduction of mole-
cules with specific properties (thermal, electrical, optic, chromogenic, pho-
tosensitive and mechanical) into polymeric matrices. The sol-gel technique
has been increasingly used to produce the functional coatings on various
forms of material. The precursors used in the preparation of the ‘sol’ are usu-
ally inorganic metal salts or metal organic compounds, such as metal alkox-
ide. The precursor is subjected to a series of hydrolysis and condensation

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42 Functional nanofibers and their applications

High-voltage

Capillary tip Polymer solution

Fiber formation

Fiber membrane
Counter electrode

3.3 The schematic views of the electrospinning setup.

reactions for the inorganic domain formation. The use of a suitable coupling
agent permits the formation of a strictly interconnected network, prevent-
ing macroscopic phase separation.53, 54 The sol-gel technique has several
advantages over other processes including its simplicity, good homogeneity,
the ease of control of the film composition, its safety, its ability to produce
large area coatings, its low processing temperature and the low cost of both
the apparatus and raw materials.55
Many interesting properties of polymer nanofibers are the result of their
extremely high surface to weight ratio in comparison to other conventional
fibrous structures. The high pore volume and tight pore sizes make nano-
fibers ideal for use in such application areas as filtration, sensors, protec-
tive clothing and functional materials. The ability to deposit well-controlled
coatings on nanofibers expands their application potential by changing both
physical and chemical properties. Nanoparticles frequently used in such
methods include TiO2 40, 41, 56 and ZnO.48

3.3.4 Electroless deposition and in situ reduction method

Initially the polymer/metal ion composite nanofibers are prepared by elec-
trospinning, before the metal ions are reduced within composite nanofibers.
For example, the Ag nanoparticles dispersed in polyacrylonitrile (PAN)
nanofibers spun by electrospinning are prepared in situ by the reduction
of silver ions in N2H5OH aqueous solution.37 The electrospun Polyamide 6
(PA6)/Cu composite nanofibers49 are prepared using an electroless deposi-
tion technique.

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 Processing of composite functional nanofibers 43

3.4 Formation of polymer and inorganic salt

composite nanofibers
Polymer/transition metal salt composite nanofibers have attracted extensive
attention primarily due to the fact that these fibers could easily be trans-
formed into polymer/metal or polymer/semiconductor composite nanofi-
bers through chemical treatment.37, 49, 57–59 Various amounts of inorganic salts
are initially added to the polymer electrospinning solutions. The composite
solution is mixed by mechanical stirring, before being electrospun to form
polymer/inorganic salts composite nanofibers. Composite nanofibers of this
nature have many potential applications, such as in photographic and opti-
cal materials, catalysis and catalyst supports, ionic conductors, sensors and
environmental protection materials.57–61 Commonly used inorganic salts
include AgNO3,37 ZnCl262and FeCl3.63

3.5 Examples and applications of composite

functional nanofibers
The application fields of electrospun polymer composite nanofibers have
been steadily expanding, particularly in recent years. The relevant US pat-
ents show that some of the best representations of this can be seen in the
fields of filtration systems and medical prosthesis, particularly in the areas
of grafts and vessels. The high aspect ratio (l/d), large available surface area,
surface morphology and potential homogeneous dispersion of nanofibers
throughout matrix-made electrospun fibers mean they are of great interest
as fillers in composite matrices. Other applications which have been targeted
included composite reinforcement, tissue templates, electromagnetic shield-
ing, composite delamination resistance and liquid crystal devices, among
others. The mechanical properties and reinforcing behavior of continuous
nanofibers differ significantly from the finite length of their conventional
counterparts (engineering fibers such as carbon, glass and Kevlar fibers) that
are used as reinforcements in composite developments. It should be recog-
nized that most of these applications have not yet reached industry level,
but are currently at a laboratory research and development stage. However,
their promising potential is believed to be attracting attention and invest-
ment from academia, government and industry all over the world.64, 65

3.5.1 Polymer and polymer composite nanofibers

Electrospinning of polymer blends is an efficient way to create composite
nanofibers that have improved material properties, such as higher tensile
strengths and wetting behavior.14, 16 The incorporation of cellulose whis-
kers into nanofibers of PEO by the electrospinning process can enhance

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44 Functional nanofibers and their applications

the mechanical properties of the PEO.66 Liu et al.16 studied the structure
and properties of poly(L-lactic acid)/poly(vinyl alcohol) composite non-
woven materials produced by co-electrospinning. The results indicate that
electrospun poly(L-lactic acid) (PLLA)/PVA nonwoven materials demon-
strate better wettability than pure PLLA electrospun fibrous web, and the
larger the ratio of PVA, the better the wettability of the composite achieved.
Chitin and chitosan have been examined and used in a wide variety of bio-
medical applications, including as drug delivery carriers, surgical sutures,
bone-healing materials and, in particular, wound dressings.67 Chitin and cer-
tain derivatives can accelerate the tensile strength of wounds by speeding
the fibroblastic synthesis of collagen in the first few days of wound healing,68
while chitosan can achieve hemostasis and promote normal tissue regenera-
tion.69 Chen et al.70 prepared a collagen/chitosan nanofibrous membrane as
a wound dressing by electrospinning. The membrane was found to promote
wound healing and induce cell migration and proliferation. From animal
studies, the collagen/chitosan nanofibrous membrane was better than gauze
and commercial collagen sponge in wound healing.
A core-sheath configuration has the potential to achieve products with
unique properties that are difficult to obtain from the constituent materi-
als if spun separately. This approach can be broadly viewed as a blending
of materials, except that the two materials maintain their separate identi-
ties, with the core material completely surrounded by the sheath material.17
Zhang, Huang and coworkers71, 72 successfully demonstrated the feasibil-
ity of preparing core-sheath nanofibers using two biodegradable materi-
als, polycaprolactone (PCL) as the sheath and gelatin as the core, with the
structures suited for use in tissue engineering and drug delivery. The authors
showed that the size of the core could be controlled by simply varying the
core polymer solution concentration. Gelatin and PCL, being natural and
synthetic polymers respectively, degrade at different rates and, therefore,
the researchers suggested that such structures will be useful in applications
such as drug delivery, which may require different delivery rates at different
times.

3.5.2 Polymer and nanoparticle composite nanofibers

The novel nanocomposite materials based on organic and inorganic spe-
cies combined at a nanoscale have attracted great attention. These organic–
inorganic hybrids have the light weight, flexibility and good moldability of
organic materials along with the high strength, heat stability and chemi-
cal resistance of inorganic materials. These composites are expected to find
applications in catalytic membranes, ultrafiltration, scratch- and abrasive-
resistant hard coatings, nonlinear optical materials, contact lenses and rein-
forcement of elastomers and plastics.65, 73, 74

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 Processing of composite functional nanofibers 45

3.4 High-resolution transmission electron microscopy (HRTEM) images

of electrospun PA6 composite nanofiber with 4 wt% Fe-OMT.

Cai et al.34–36 prepared polymer/organic-modified Fe-montmorillonite

(Fe-OMT) composite nanofibers and studied the structure, morphology
and performances. The results showed the silicate clay layers to be well
dispersed within the composite nanofibers as well as almost aligned along
the axis of the nanofibers. The dispersion of Fe-OMT within PA6 compos-
ite nanofibers is characterized by high-resolution transmission electron
microscopy images, as showed in Fig. 3.4. The loadings of Fe-OMT nota-
bly increase the thermal stability, flammability and mechanical properties
of composite nanofibers. The crystalline properties of the PA6 compos-
ite nanofibers were also investigated by the wide-angle x-ray diffraction
(XRD). Figure 3.5 demonstrates that the presence of nanoclays improves
the γ-form crystals and induces the formation of α-form crystals of the
PA6. It may be suggested from this that the nanosize clay platelets act as
effective nucleating agents and promote the heterogeneous nucleation of
PA6.34 Shao et al.48 prepared PAN nanofibers by electrospinning, before a
functional layer of ZnO was deposited onto the surface of PAN nanofibers
using sol-gel techniques. The ZnO coated PAN nanofibers were carbon-
ized to form functional carbon nanofibers, and the surface structures of
the functional carbon nanofibers were characterized by XRD and scan-
ning electron microscopy (SEM). The SEM images of ZnO coated PAN
nanofibers, preoxidized ZnO coated PAN nanofibers and carbon/ZnO
nanofibers are shown in Fig. 3.6. SEM observations revealed that the ZnO
was firmly and clearly distributed on the surface of carbon nanofibers as

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46 Functional nanofibers and their applications

400

300
Relative intensity

200

PA6/Fe-OMT4
100
PA6/Fe-OMT2
PA6
0

10 15 20 25 30 35 40
2 Theta (degrees)

3.5 Wide-angle XRD patterns of electrospun PA6 nanofiber and PA6/

Fe-OMT composite nanofibers.

nanoclusters (about 100 nm). In addition, XRD examination showed that

the ZnO nanoclusters had a perfect crystalline structure, while the carbon
nanofibers were of amorphous structure. The results indicate that sol-gel
coating treatment has profound effects on the surface structure of carbon
nanofibers.
Wu et al.40, 41 studied Polyvinyl acetate (PVAc)/TiO2 hybrid nanofibers by
combining the sol-gel process with electrospinning technology, using PVAc
as an organic segment and TiO2 as an inorganic part. The SEM images indi-
cated that the average diameter of the electrospun PVAc/TiO2 nanofibers
increased after hybridization. From the atomic force microscopy (AFM)
and transmission electron microscopy (TEM) analysis, it could be con-
cluded that the inorganic hydrolysis products lead to the formation of the
particle-like surface morphology of hybrid nanofibers. It was also found
from the viscosity measurement and Fourier transfer infrared (FTIR)
analysis that newly associated hydrogen bonds were formed between the
organic and inorganic components in hybrid nanofibers. The influences of
TiO2 content on the thermal stability and mechanical properties of PVAc/
TiO2 nanofibers are shown in Figs 3.7 and 3.8. The thermogravimetrical
analysis (TGA) and tensile property analysis revealed that the thermal
stability and strength were enhanced as the TiO2 content increased. It can
be reasonably concluded that hydrogen bonds or other coordinate bonds
were formed in the nanofibers between the TiO2 inorganic network and the
polymeric chains.

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 Processing of composite functional nanofibers 47

(a)

(b)

(c)

3.6 SEM images of (a) ZnO coated PAN nanofibers, (b) pre-oxidized
ZnO coated PAN nanofibers and (c) carbon/ZnO nanofibers.

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48 Functional nanofibers and their applications

100 18
c
16
b
80
Weight loss (wt.%) a 14 c
b
12
60 a
450 500 550 600 650 700

40

20

100 200 300 400 500 600 700 800

Temperature (ºC)

3.7 TGA curves of PVAc hybrid nanofibers with different TiO2 content:
(a) 0 wt%, (b) 0.36 wt% and (c) 0.72 wt%.

400 52
380 50
360 48
Break strength (cN/mm2)

340

Break elongation (%)

46
320
44
300
42
280
40
260
38
240
220 36

200 34

0.00 0.36 0.72

TiO2 content (wt%)

3.8 Mechanical properties of PVAc/TiO2 nanofibers with different TiO2

contents.

3.5.3 Polymer and inorganic salt composite nanofibers

Polymer/inorganic salts composite nanofibers have many potential appli-
cations, including in photographic and optical materials, catalysis and
catalyst supports, ionic conductors, sensors and environmental protection
materials.57–61

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 Processing of composite functional nanofibers 49

Ji et al.62 explored the electrospinning of PAN/ZnCl2 composite nanofi-

bers and the response of these nanofibers to H2S. The ZnCl2 in composite
nanofibers could react with H2S to form ZnS crystals on the fiber surface.
ZnCl2-added polymer nanofibers have potential use in sensing and remov-
ing H2S, which is colorless, flammable, heavier than air and dangerous to the
environment and human health. In addition, ZnCl2-added polymer nanofi-
bers are excellent precursors for the preparation of nanofibers containing
ZnS. The unique catalytic and semiconducting properties of ZnS75–77 mean
that such nanofibers have great potential for new applications in a wide
variety of areas, including as catalysts and in electronic and optoelectronic
nanodevices. Cai et al.63 prepared PAN/FeCl3 composite nanofibers using a
simple compounding and electrospinning technique. The results indicated
that the FeCl3 loading reduced the diameter of composite nanofibers, while
increasing their thermal stability properties. It was also found from shake
flask tests that the reduction percentage of tested bacteria Escherichia coli
reached 87% for the PAN composite nanofibers with 5 wt% FeCl3, due to
the sterilization effects of the transition metal halide FeCl3.

3.6 Future trends

Electrospinning is a simple, versatile method for creating polymer-based
high-functional and high-performance nanofibers that could revolutionize
the world of structural materials. Other functional molecules, biomolecules
or nanoparticles can easily be incorporated into electrospinning solutions
to generate a combination of nanofiber functionalities.65 However, the pro-
cessing and practical application of composite nanofibers have so far been
rather limited, and most have only been considered as potential applica-
tions in the future.

3.7 Acknowledgments
This chapter was financially supported by the National Natural Science
Foundation of China (No. 51006046), the Natural Science Foundation of
Jiangsu Province (No. BK2010140) and the Research Fund for the Doctoral
Program of Higher Education of China (No. 200802951011 and No.
20090093110004).

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