Polymer-Plastics Technology and Engineering

ISSN: 0360-2559 (Print) 1525-6111 (Online) Journal homepage: http://www.tandfonline.com/loi/lpte20

Functional Copolymer/Organo-MMT
Nanoarchitectures: XXVI. Fabrication and
Characterization of Electrospun Nanofibers from
PCL/ODA-MMT and Copolymer-g-PLA/ Ag-MMT
Blends

Zakir M. O. Rzayev, Murat Şimşek & Kouroush Salimi

To cite this article: Zakir M. O. Rzayev, Murat Şimşek & Kouroush Salimi (2015) Functional
Copolymer/Organo-MMT Nanoarchitectures: XXVI. Fabrication and Characterization of Electrospun
Nanofibers from PCL/ODA-MMT and Copolymer-g-PLA/ Ag-MMT Blends, Polymer-Plastics
Technology and Engineering, 54:16, 1723-1734, DOI: 10.1080/03602559.2015.1050512

To link to this article: https://doi.org/10.1080/03602559.2015.1050512

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Polymer-Plastics Technology and Engineering, 54: 1723–1734, 2015
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print/1525-6111 online
DOI: 10.1080/03602559.2015.1050512

Functional Copolymer/Organo-MMT Nanoarchitectures:

XXVI. Fabrication and Characterization of Electrospun
Nanofibers from PCL/ODA-MMT and Copolymer-g-PLA/
Ag-MMT Blends
Zakir M. O. Rzayev1, Murat Şimşek1, and Kouroush Salimi2
1
Institute of Science & Engineering, Nanotechnology and Nanomedicine Division, Hacettepe University,
Beytepe, Ankara, Turkey
2
Department of Chemical Engineering, Faculty of Engineering, Hacettepe University, Beytepe, Ankara,
Turkey

GRAPHICAL ABSTRACT

We synthesized poly(e-caprolactone)/octadecyl amine-montmorillonite clay nanocomposite as

a matrix polymer by solution intercalative method and new amphiphilic poly(maleic
anhydrde-alt-1-octadecene)-g-poly(L-lactic acid)/Agþ-montmorillonite clay nanocomposite
as a partner polymer by interlamellar graft copolymerization of lactic acid onto anhydride
copolymer in the presence of silver salt of montmorillonite clay as catalyst-nanofiller. Novel
polymer nanofibers were fabricated by electrospinning of matrix/partner blends with
different volume ratios. The nanocomposites and nanofibers were investigated by Fourier
transform infrared spectroscopy, thermal gravimetric analysis–differential scanning

Address correspondence to Zakir M. O. Rzayev. Hacettepe University, Beytepe Campus, Institute of Science and Engineering, Nanotech-
nology and Nanomedicine Division, Ankara, Turkey. E-mail: rzayevzmo@gmail.com
Color versions of one or more of the figures in this article can be found online on at www.tandfonline.com/lpte

1723
1724 Z. M. O. RZAYEV ET AL.

calorimetry, and scanning electron microscope–transmission electron microscope methods.

The diameters, morphologies, and thermal behavior of fibers were strongly depended on
the partner-polymer nanocomposites loadings. The fabricated biocompatible and
biodegradable nanofibers can be utilized for biomedical and filtration applications.

Keywords Ag-MMT; Copolymer-g-PLA; Electrospinning; Nanocomposites; Nanofibers;

Organoclay; PCL

INTRODUCTION alternating copolymers of maleic anhydride in the presence

Among several fiber-manufacturing techniques such as of Agþ-MMT has been not investigated.
electrospinning, phase separation, selfassembly, and drawing It was proposed that morphology control in the chosen
electrospinning from solutions of the surfactant-stabilized systems strongly depends on many factors, such as the utilized
polymer blends/nanoparticles systems[1,2] is widely investi- synthetic method for preparation of nanocomposites, chemical
gated owing to many advantages: simplicity and inexpensive and physical structures, the tendency to selfassembly via
nature of electrospinning setup[3], a continuous process for
the production of polymer fibers, controllability of operational
parameters, and diversity achieved by altering the solution
properties to control the phase separation process[4].
Aliphatic biodegradable polyesters such as poly(e-caprolac-
tone) (PCL), poly(lactic acid) (PLA), their copolymers and com-
posites/nanocomposites were widely used in biomedical and
industrial application[5–12]. The synthesis and characterization
of PCL/clay nanocomposites, especially their structures and the
states of dispersion of the silicate platelets in the PCL matrices
were reported by many researchers[13–17]. Marras et al.[18] showed
that addition of inorganic filler facilitated the formation of fine
electrospun PCL/montmorillonite (MMT) clay fibers with fewer
bead defects and narrower fiber-size distributions. In a study, bio-
degradable-multiblock copolymers from PCL/PLA displayed
enhanced mechanical properties with ultimate tensile strength
[19]
. Nanoscale clay particles were incorporated in electrospun
PLA fibers to control modulus and biodegradation rate for poten-
tial biodegradable packaging applications[20].
Though poly(maleic anhydride-alt-1-octadecene) has been
known for a long time[21,22], its industrial production has only
been recently realized. Now, it is a new commercially avail-
able polymer with a wide range of usages such as release coat-
ings, anticorrosive agents, chelant/surfactant, and cross-linker
for epoxide- and hydroxyl-functionalized polymers[23],
water-soluble colloidal nanocrystals with various composi-
tions, morphologies, and sizes. Alternating copolymers like
poly(maleic anhydride-alt-1-octadecene) with longer hydro-
phobic branches and their diamine cross-linked networks[24,25]
provide a stable nanoparticle shell and hydrophobic double
layer as well as water solubility of nanoparticles.
Ag-nanoparticles have been widely used in filters, sensors,
and biomedical areas due to their high surface area, excellent
biocompatibility, and easy synthesis methods[26–30]. However,
the fabrication of biodegradable polymer–organoclay/maleic
anhydride alternating copolymer/Agþ-MMT (silver salt of
MMT) nanocomposites and nanofibers has not been reported.
FIG. 1. Schematic representation of the synthetic pathways for the matrix
Although, despite being the most promising reaction for the and partner polymer nanocomposites and fabrication of nanofiber webs (elec-
synthesis of polymer/clay nanocomposites, the interlamellar trospinning setup). Note: PCL, poly(e-caprolactone); ODA-MMT, octadecyl
graft copolymerization of lactic acid (LA) monomer onto amine-montmorillonite.
 PCL/ODA-MMT AND COPOLYMER-g-PLA/Ag-MMT NANOFIBERS
H-bonding, hydrophobic/hydrophilic balance, functionality and
molecular weights of matrix polymers, the origin of used nano-
fillers, as well as the type of in situ interfacial interactions and
the interfacial adhesive strength. Taking into consideration these
important factors, we have developed a new approach for the
synthesis of polymer nanofibers by electrospinning using PCL
and poly(maleic anhydride-alt-1-octadecene)-g-poly(L-lactic
acid) (copolymer-g-PLA) as matrix-partner polymer systems,
reactive octadecyl amine-montmorillonite (ODA-MMT) and
Agþ-MMT clays as nanofillers, and various volume ratios of
binary polymer blend solutions in dimethylformamide (DMF)/
chloroform (CHCl3). We conducted the investigation of the
complex multistep mechanisms in the formation of nanostruc-
tural fibers containing two types of silicate layered clays, such
as organoclay and silver salt of MMT clay, which allowed us
to design and fabricate a qualitatively improved new generation
of nanofibers with controlled morphology. General synthetic
pathways of matrix-partner polymer nanocomposites and the
fabrication of nanofıbers (electrospinning setup) are schemati-
cally represented in Figure 1.
EXPERIMENTAL
Materials
Poly(e-caprolactone) (Mw ¼ 125.000 Da, Mn ¼ 80.000 Da,
and PDI ¼ 1.56), commercially available poly(maleic
anhydride-alt-1-octadecene) (copolymer), Mn ¼ 40.000 g/
mol, density 0.92 g/cm3 and softening temperature ∼120°C),
Naþ-MMT (MMT K-10, surface area 220–270 m2/g), ODA-
MMT (Nanomer I.30E) with content of octadecyl amine 25–
30%, bulk density 0.41 g/cm3, and crystallinity 52.8% (by
XRD), L-lactic acid (analytical standard) and AgNO3 (ACS
reagent, assay ∼99%, m.p. 212°C with decomposing) were
purchased from Sigma-Aldrich. DMF, chloroform, and all other
solvents and reagents were of analytical grade and used without
purification.
Synthetic Procedures
Synthesis of individual components for the nanofiber com-
posites includes the following important steps: (1) preparation
of PCL/ODA-MMT (3.2 wt%) layered silicate nanocomposite
(NC-1) as a matrix polymer by intercalating the PCL chains
between silicate galleries in DMF solution at 80°C for 8 h with
intensive mixing in carousel type of microreactor until the for-
mation of a homogenous viscous product. The nanocomposite
was isolated by precipitation with ethanol, extracted by centri-
fugation and dried under vacuum at 60°C; (2) the preparation
of silver salt of MMT clay (Agþ-MMT) was carried out by
ion-exchange reaction of Naþ-MMT and AgNO3 in pure water
with intensive mixing at room temperature for 3 h until the for-
mation of a homogenous viscous medium. The silver-enriched
MMT clay in the form of a gray color powder was isolated by
precipitation with ethanol, dried under vacuum at 60°C and
then annealed at 150°C for 10 min; (3) second nanocomposite
1725
(NC-2) was synthesized by interlamellar bulk graft copolymer-
ization of LA monomer onto poly(maleic anhydride-alt-1-
octadecene) as a partner polymer in the presence of
Agþ-MMT (5%) as a catalyst-nanofiller in LA solution under
vacuum (600 mm/Hg) at 80  0.1°C for 6 h using a specially
constructed microreactor supplied with Dean-Star unit. After
the formation of a homogeneous viscous solution, the reaction
mixture was treated with a large amount of ethanol with inten-
sive mixing up to full precipitation of the powder product,
which was isolated by filtration and ultracentrifugation, and
dried under vacuum at 40°C; (4) the matrix polymer (NC-1)-
partner polymer (NC-2) solutions (5 mL for each system with
20% concentration) were prepared by intensive mixing in
DMF and CHCl3 solutions at 40 and 80°C, respectively, until
the formation of a fully homogenized viscous liquid; (5) NC-1/
NC-2 blend solutions with various volume ratios (10:0, 9:1,
8:2, and 6:4) were prepared by intensive mixing for further uti-
lization in the electrospinning processing.
Fabrication of Nanofibers
NC-1/NC-2 nanofibers were fabricated by the electrospin-
ning method using various volume ratios of the solution blends
of matrix-partner polymer-layered silicate nanocomposites. In
brief, 3 mL NC-1 (20%) in DMF and 2 mL NC-2 (20%) in
CHCl3 were mixed until complete dissolution at room tem-
perature for preparing NC-1/NC-2 (6/4). Then, the polymer
solution was loaded into a 5-mL plastic syringe equipped with
a stainless steel needle. To prepare nanofibers, electrospinning
was performed using the following operational parameters: a
syringe pump with a 21-gauge needle (NE 300, New Era Pump
Systems) was fixed vertically to obtain a steady flow at a flow
rate from 0.2 to 3.0 mL/h; a high voltage (Gamma High
Voltage Research) of 6–25 kV was applied at various distances
of 8–25 cm between the tip of the needle and the grounded
collector. Randomly oriented fibers were obtained by
collecting the fibers onto an aluminum foil fixed on a station-
ary collector. Nanofibers from NC-1 and NC-1/NC-2 solution
blends with volume ratios of 9/1 (NFC-1), 8/2 (NFC-2), and 6/
4 (NFC-3) were fabricated in the optimized electrospun
conditions.
Characterizations
The Fourier transform infrared (FTIR) spectra were
recorded on a FTIR Thermo-Nicolet 6700 spectrometer in
the range of 4000–500 cm1 with a resolution of 4 cm1.
To identify the chemical/elemental analysis of Ag-MMT
nanoparticles, scanning electron microscope (SEM)/EDX
(JSM-6400 JOEL) with an acceleration voltage of 20 kV was
used. The surface morphology of the nanofillers, nanocompo-
sites, and nanofibers were examined using a brief description
of the ZEISS SUPRA 40 field emission scanning electron
microscopy with image scales: 1, 2, and 10 µm, magnification
x 1.000–50.000, and an acceleration voltage of 20 kV. All
1726 Z. M. O. RZAYEV ET AL.

specimens were freeze-dried and coated with a thin layer of
gold before testing by using a QUORUM-Q150 R ES surface
coating device. The average diameter of the fibers were cal-
culated by analyzing SEM images of minimum a hundred
individual fibers with Image J software (NIH) for each
sample.
Transmission electron microscopy (TEM) internal mor-
phology images were performed by FEI Tecnai G2 Spirit Biot-
win Model High Contract Transmission Electron Microscopy
(STEM) with Lantan Hexaboron Gun at 120 kV. The powder
polymer sample was dispersed in ethanol with 0.1% concen-
tration, and then sonicated up to the formation of a homoge-
neously dispersed solution. The prepared solution (3–5 µL)
was dropped on the surface of carbon coated grid and dried
until the formation of full solid phase on a grid surface before
testing.
Thermogravimetric (TGA-DTG) analyses were performed
using EXTRAR600 TG-DTA6300 Thermal Analyzer and at
a linear heating rate of 10°C/min under nitrogen flow. The
samples were measured in a sealed alumina pan with a mass
of about 10 mg.
RESULTS AND DISCUSSION
Synthetic Pathways
Lactic acid (co)polymers are commonly synthesized by
well known condensation (step polymerization) and graft poly-
merization methods. The reaction requires tin-containing com-
pounds as catalysts and mineral acid, preferable sulfuric acid
or dimethylsulfoxide (DMSO) as a water absorbent, and is car-
ried out at high temperatures for a long time due to the low
reactivity of LA monomer. In this work, we applied a new
approach for the synthesis of copolymer-g-PLA/Ag-MMT by
bulk interlamellar graft copolymerization of LA monomer onto
poly(maleic anhydride-alt-1-octadecene) copolymer in the
presence of Agþ-MMT as a catalyst-nanofiller and DMSO
under vacuum at 80°C until rapid phase separation (28 min).
Under similar condition, we also carried out graft copolymer-
ization in the presence of Naþ-MMT clay as an isostructural
analogue of Agþ-MMT. It was observed that Naþ-MMT also
exhibited catalytic effect while phase separation time increased
to 40 min. In the following experiments, we preferred the use
of the novel Agþ-MMT clay which has the following impor-
tant advantages: (1) the formation of silver nanoparticles dur-
ing in situ processing and by thermal treatment, (2) accelerated
phase separation in both the synthesis of nanocomposite graft
copolymer and nanofiber fabrication, and (3) increased bio-
compatibility and bioactivity of nanofiber webs, which is very
important for their further bioengineering applications.
Polymer Nanofibers via Electrospinning
Electrospinning is a fascinating technology to produce
nano- and micro-sized fibers from polymer solutions. It
enables the use of a vast range of polymers and polymer
blends. Therefore, nano-sized fillers can be incorporated into
polymers to improve their properties for various applications
such as tissue engineering, nanomedicine, pharmacy, bioengi-
neering and filtration. A typical electrospinning process is
shown in Figure 1 (bottom). Characterization of electrospun
fibers was performed by a SEM. To obtain stable and bead-
free nanofibers, the electrospinning parameters including poly-
mer concentration, voltage, flow rate, distance between the tip
of the needle and the collector were optimized. The solvent
choice and the concentration of polymer solution are important
factors contributing to the production of stable fibers in the
electrospinning process. The most suitable concentration to
obtain a stable polymer jet of NC-1/NC-2 blends was 20%.
The use of DMF as a polar solvent for the matrix polymer
nanocomposite essentially increased the conductivity (dielec-
tric constant is 36.71 for DMF and 4.81 for chloroform)[31]
and surface tension of the polymer solution, and therefore,
improved electrospinnability of polymer through accelerating
the phase separation process in the formation of nanofiber
mats. Similar effects can be realized in the positive charged
ODA-MMT and Ag-MMT clays in the studied systems. The
optimal conditions for the fibers and their distributions are
summarized in Table 1.
Chemical Structures of Nanofibers
In this study, FTIR spectroscopy was utilized to confirm the
chemical structures of the nanofibers with various composi-
tions, especially complexation of octadecyl amine-intercalant
with PCL matrix polymer and silver salt of clay with the

TABLE 1
Nanofiber composition-e-spun parameters-diameter relationships

Composition of nanofibers Ratio (mL, v/v) Voltage (kV) Distance (cm) Flow rate (mL/h) Diameter (nm)
PCL/ODA-MMT (NC-1) 10/0 8 15 0.2 159  56
(NC-1)/copolymer-g-PLA 8/2 8 15 0.2 212  151
(NC-1)/(NC-2) 9/1 6 10 0.3 405  208
8/2 313  145
6/4 252  82
PCL, poly(e-caprolactone); ODA-MMT, octadecyl amine-montmorillonite; NC, nanocomposites.
 PCL/ODA-MMT AND COPOLYMER-g-PLA/Ag-MMT NANOFIBERS 1727

FIG. 2. FTIR spectra (thin film) of electrospun nanofiber composites (NFC)s with different compositons of matrix-partner nanocomposites: PCL/ODA-MMT
poly(maleic anhydride-alt-1-octadecene)-g-PLA/Ag-MMT with volume ratio of matrix/partner nanofiber composites: NFC-1 (9/1 v/v), NFC-2 (8/2 v/v) and
NFC-3 (6/4 v/v). Note: PCL, poly(e-caprolactone); ODA-MMT, octadecyl amine-montmorillonite; NFC, nanofiber composites.

FIG. 3. (a) XRD patterns and X-ray reflection parameters and (b) SEM/EDX composition elemental analysis of Ag-MMT clay. Note: MMT, montmorillonites.
1728 Z. M. O. RZAYEV ET AL.

partner graft copolymer via –C ¼ O … NH2–, –COOH …

NH2– and –COOH … Ag-MMT complex-formations, respect-
ively. The obtained results are illustrated in Figure 2. The ester
carbonyl and carboxyl groups from both polymer systems were
highly responsive to ionic interactions. Octadecyl amine and
silver ions tended to coordinate with carbonyl and carboxyl
groups of PCL, maleate/carboxyl groups of the copolymer-g-
PLA macromolecules. All these interactions are responsible
for the formation of selfassembled structures in the nanofibers.
The absorption region of the carbonyl group of pristine PCL
appears around 1800–1650 cm1[32]. The characteristic peaks
at 1722 (s) cm1 were associated with the ester C ¼ O groups
of PCL and PLA fragments. A broad peak appeared at 1596
(m) cm1 whose intensity increased with the increasing
amount of the partner polymer in nanofiber compositions con-
taining both the carboxyl and silver nanoparticles. Moreover,
the absorption band at 1596 cm1 in nanofiber composition
(NFC-1) shifted to lower wavenumber regions (1583 and
1570 cm1) in NFC-2 and NFC-3 as a result of physical inter-
actions between functional groups of the matrix and the part-
ner polymer macromolecules. This observation is consistent
with the formation of the above mentioned hydrogen bonded
and coordinated complexes in the nanofiber structures. FTIR
spectra also contained the characteristic bands for the CH2
and CH3 groups (2922, 2863, 1457, 1415, and 1366 cm1),
Si–O stretching (1087 cm1), and C–O ester groups
(1167 cm1).

Physical Structures of Nanofibers

FIG. 4. XRD patterns of (a) NFC-1, (b) NFC-2, and (c) NFC-3 nanofibers.
X-ray diffraction (XRD) analysis was performed to evalu-
Effect of loading the partner polymer nanocomposite. Note: NFC, ate the physical structures, X-ray reflection parameters and
nanocomposites. amorphous and crystallinite areas of nanofillers and their

FIG. 5. SEM images of ODA-MMT (left images) and Ag-MMT (right images). Note: ODA-MMT, octadecyl amine-montmorillonite.
 PCL/ODA-MMT AND COPOLYMER-g-PLA/Ag-MMT NANOFIBERS
FIG. 6. SEM images of microporous poly(maleic anhydride-alt-1-octade-
cene)-g-PLA/Ag-MMT nanocomposite containing in situ generated AgNPs.
Note: PLA, poly(lactic acid); NPs, nanoparticles; MMT, montmorillonites.
nanocomposites and nanofiber mats. XRD patterns and X-ray
reflection parameters of crystallinite peaks from Ag-MMT
clay, as well as SEM/EDX composition-elemental analysis
results for Ag-MMT are given in Figure 3a and 3b, respect-
ively. The well-known Scherrer equation was used to calculate
the crystallite size (τsh, the mean thickness) of the coherent
FIG. 7. TEM morphologies of (a, b, c, and d) poly (maleic anhydride-alt-1octadecene) copolymer and (e and f) poly(maleic anhydride-alt-1-octadecene)-g-
PLA/Ag-MMT nanocomposite. Note: PLA, poly(lactic acid); NPs, nanoparticles; MMT, montmorillonites.
1729
scattering domain of crystals from XRD full width data at half
maximum (FWHM) intensity:
s ¼ Ksh k=bcosh ð1Þ
where: Ksh is a Scherrer constant (0.89)[33]; τ is the mean size
of the ordered (crystalline) domains, which may be smaller or
equal to the grain size; k is the X-ray wavelength
(1.5406 nm); b is the line broadening at FWHM, after
subtracting the instrumental line broadening, in radians.
Agreeing with the XRD patterns (Fig. 3a), pristine Ag-
MMT clay exhibited two reflection peaks from silicate layers
at 5.29°2h (d002 ¼ 16.68 Å) and 8.83°2h (d003 ¼ 10.0 Å) from
–Si-OH at edges with crystallite sizes of 1.98 and 0.76 nm,
respectively. The crystal peaks at 39.36° and 45.44°2h with
1.13 and 0.48 nm sizes can be attributed to in situ generated
silver cub crystals nanoparticles[34] in Ag-MMT composition
after its annealing at 150°C for 5 min under nitrogen flow.
Very strong peak at 26.54°2h with lower crystallite size
(0.49 nm) can be interpreted by transfer of Ag-precursor to
amorphous colloidal state during synthetic procedure of used
organoclay and Ag-MMT clay.
The results of elemental analysis of Ag-MMT clay
composition (Fig. 3b) confirmed the effective exchange
reaction between Na and silver cations and formation of inter-
calated silver particles with mass of 5.83% as well as essential
reducing of mass for Na(0.18%) in Ag-MMT clay.
It is known that pristine powder PCL exhibits the semicrys-
talline structure with the reflection peaks at 21.4° and 23.6°2h,
which are attributed to the orthorhombic planes (110 and
200)[35]. The XRD patterns and reflected peak parameters of
1730 Z. M. O. RZAYEV ET AL.

FIG. 8. SEM micrographs of the electrospun PCL/ODA-MMT (NC-1), (NC-1)/poly(maleic anhydride-alt-1-octadecene)-g-PLA (graft copolymer), and NC-1/
copolymer-Ag-MMT (NC-2) nanofibers with their diameter distributions. The effect of copolymer and Ag-MMT clay. Note: PLA, poly(lactic acid); NPs, nano-
particles; MMT, montmorillonites; PCL, poly(e-caprolactone); ODA-MMT, octadecyl amine-montmorillonite; NC, nanocomposite.

matrix/partner polymer nanofiber composites (NFC-1, NFC-2,
and NFC-3) are given in Figure 4. The presence of X-ray
reflection peaks at 21.52 and 23.85°2h with d-spacing values
of 4.15 and 3.73 Å was associated with orthorhombic planes
(110 and 200) from PCL matrix in nanofiber composites
(Fig. 4a). The intensity and area of first peak at 21.52°2h
visible increased with increasing the partner nanocomposite
fraction in nanofiber mats due to an increase in amount of
grafted PLA side-chain branches. The comparative analysis
showed that the nanofiber composites exhibited semicrystal-
line structures with predominantly amorphous areas, which
were increased by loading the partner nanocomposite. The
presence of X-ray reflection weak crystal peaks at 35.51 and
44.25°2h (Fig. 4a) and 34.42°2h (Fig. 4b) can be related to
cub crystals from in situ generated and dispersed AgNPs onto
nanofiber mats. Moreover, these peaks disappeared in XRD pat-
terns of nanofiber mats prepared using 6/4 volume ratio of
matrix/partner polymer solution blend (Fig. 4c) as a result of
transfer silver nanoparticle to amorphous colloidal state. Similar
changes were observed for the crystal peaks in the XRD patterns
of silicate region around 1.0-10°2h.
Morphology of Nanofillers and Partner Nanocomposites
Scanning electron microscope images of organic (ODA-
MMT) (Fig. 5a and 5b) and inorganic (Ag-MMT) clays (Fig.
5c and 5d) showed different surface morphological structures.
 PCL/ODA-MMT AND COPOLYMER-g-PLA/Ag-MMT NANOFIBERS 1731

FIG. 9. Comparative SEM morphology analysis of NC-1/NC-2 nanofibers. The effect of partner polymer nanocomposite (NC-2) loading.
1732 Z. M. O. RZAYEV ET AL.

TABLE 2
TGA-DTG analysis of degradation (Td and weight loss)
parameters of nanofiber webs

NC-1/
NC-2 Degradation Td(onset) Td(max) Td(outset) Weight loss
(v/v) steps (°C) (°C) (°C) (%)

9/1 Step-1 114.42 211.8 267.31 18.28

Step-2 267.31 327.4 378.85 36.80
Step-3 378.85 435.1 505.77 22.72
8/2 Step-1 112.87 354.2 306.93 52.86
Step-2 306.93 428.8 512.87 31.81
6/4 Step-1 117.82 355.7 395.60 58.25
Step-2 395.60 430.3 501.98 23.64
TGA-DTG, thermogravimetric analysis; NC, nanocomposites.

Figure 6 shows SEM morphology images from surface

of poly(maleic anhydride-alt-1-octadecene)-g-PLA/Ag-MMT
(5%) nanocomposite containing in situ generated silver nano-
particles (AgNPs) with various geometrical nanostructures and
surface microporous structures. These observed structures are
separately given in Figure 6 (right images) in the form of mod-
els relating to AgNPs and micropores.
The TEM internal morphology of poly(maleic anhydride-alt-1-
octadecene) showed dispersed micro and nano size spherical selfas-
sembled and partially agglomerated core–shell microparticles in the
background of numerous nanoparticles (Fig. 7a–d) due to amphi-
philic-surfactant structure of alternating copolymer with hydro-
phobic/hydrophilic balance. While morphology of copolymer-g-
PLA/Ag-MMT formed mixture of the spherical selfassembled
encapsulated core (inorganic phase)–shell (graft copolymer) micro
and nanoparticles (Fig. 7e) via strong physical interfacial interac-
tions, its surface included intercalated silicate layers (Fig. 7f). The
diameter of these particles changed around 200–300 nm for the
microparticles and 30–100 nm for the nanoparticles.

Morphology of Electrospun Nanofibers

FIG. 10. TGA-DTG curves of electrospun (a) NFC-1, (b) NFC-2, and (c)
NFC-3 nanofibers prepared from solution blends of matrix/partner polymer
nanocomposites.
The organoclay exhibited better dispersion of microparticle
domains (around 5–10 nm) with spherulite-like encapsulated
core (inorganic phase)–shell (organic surfantant) structures.
Inorganic clay (Ag-MMT) exhibited fine dispersed microparti-
cles with relative low particle size of domains.
Scanning electron microscope analysis was used to investi-
gate morphologies of nanofiber mats and their diameter distri-
butions, as well as effect of a partner polymer nanocomposite
on the fiber morphology. To evaluate the effect of Ag-MMT,
and therefore the effect of volume ratios (v/v) of NC-1/NC-2
(9/1, 8/2, and 6/4), on the matrix/partner (NC-1/NC-2) nanofi-
ber morphology, we also fabricated and investigated PCL/
ODA-MMT matrix nanocomposite and poly(maleic anhy-
dride-alt-1-octadecene-g-PLA) partner polymer not containing
Ag-MMT. SEM micrographs of these fibers are illustrated in
Figure 8a–c and Figure 8d–f. The NC-1nanofibers exhibited
a cross-sectional ribbon-like and branched morphology due
to a lower degree of phase separation (Fig. 8a–c). However,
the fiber morphologies significantly improved with the
addition of partner polymer to matrix polymer in the absence
 PCL/ODA-MMT AND COPOLYMER-g-PLA/Ag-MMT NANOFIBERS
(Fig. 8d–f) and in the presence of Ag-MMT (Fig. 8g–i) exhi-
biting highly condensed cross-section morphology.
The effect of volume ratios of NFCs on fiber morphologies
and diameters was also investigated for the same electrospin-
ning condition (Table 1). Comparative analysis of nanofiber
images for the visualization of nanofiber structures exhibited
the effect of the partner polymer (Fig. 8g–i and Fig. 9). It
was observed that not only fiber diameter decreased, but also
the fiber morphology and diameter distribution improved with
increasing the ratio of Ag-MMT and multifunctional group
sites, which could easily interact with matrix polymer
(NC-1) during in situ processing, and therefore, essentially
accelerated the phase separation process during the formation
of nanofibers. The best nanofibers were obtained for the
PCL/ODA-MMT clay (NC-1) and its blends with 6/4 (v/v)
ratio.
Thermal Degradation Behaviors of Nanofibers
The results of TGA-DTG analyses are given in Figure 10
and summarized in Table 2. As seen from comparative analy-
sis of thermal behaviors of nanofiber composites with different
compositions, the obtained degradation steps strongly
depended on the content of copolymer-g-PLA/Agþ-MMT
(NC-2). Nanofibers containing relatively low content of the
partner polymer (NC-2) exhibited three step degradations
(Fig. 10a), where the first step was associated with elimination
of absorbed water and partial decarboxylation of maleate and
end LA units (total weight loss 18.28%), the second step
was related to chain degradation of the organic part (graft
copolymer, PCL, and octadecyl amine intercalant) of the com-
posite, and the third step can be related to elimination of crys-
tallized water from both clay platelets (inorganic Agþ-MMT
and organic ODA-MMT clays). However, nanofibers contain-
ing relatively high amount of NC-2 exhibited a two steps
degradation process, which can be explained by the increase
in interfacial physical and chemical interactions in the reactive
blends through carboxyl groups and octadecyl amine interca-
lant during in situ processing. Thus, an increase in NC-2 load-
ings significantly improved the thermal stability of the
nanofibers; Td(max) increased from 327 up to 430°C, while
weight loss decreased from 36.8 to 23.6% (Table 2).
CONCLUSION
We developed a facile and effective strategy for the design
and synthesis of a biocompatible poly(maleic anhydride-alt-1-
octdecene)-g-PLA/Agþ-MMT clay nanocomposite as a partner
component for the fabrication of reinforced nanofibers by
interlamellar graft copolymerization of L-lactic acid onto
maleic anhydride amphiphilic copolymer in the presence of
Agþ-MMT as a catalyst-nanofiller. Nanofibers with fine distri-
bution parameters were fabricated using biodegradable PCL/
organoclay nanocomposite as a matrix polymer by electrospin-
ning. We demonstrated that the matrix and the partner
1733
polymers containing physically and chemically responsive
functional groups tended to undergo selfassembly through
the formation of various complexes in the blend solutions,
which played an important role in the mechanism of the forma-
tion of nanofiber webs, especially in the phase separation pro-
cessing. It was observed that increasing the loadings of the
partner polymer significantly improved the morphology and
thermal behavior of the nanofiber webs. High performance
nanofibers were fabricated using a 6/4 volume ratio of the
matrix/partner polymer nanocomposite solutions. The silver
salt of MMT clay fragments of the partner polymer essentially
accelerated the phase separation process and improved the
morphology, distribution, and nanosize level of the nanofibers.
Moreover, silver nanoparticles, which were conveniently
formed by thermal treatment of the polymer systems, influ-
enced the controlled elimination of water molecules and LA
monomers from solution during phase separation, and there-
fore, contributed to the formation of microporous structures.
It was concluded that a better fundamental understanding of
the mechanisms in the formation of nanostructured fibrous
polymer materials incorporated with various nanofillers,
especially ODA-MMT and Ag-MMT clays allowed us to
design and fabricate new generation of biodegradable and bio-
compatible nanofibers with controlled morphology and
improved properties. Thus fabricated novel nanofibers can be
utilizable in a wide array of applications in bioengineering,
pharmacy, nanomedicine, nanomicrobiology, water purifi-
cation, filtration, and other engineering processing. These
topics will be the focus of our future investigations.
FUNDING
The authors thank the Turkish Scientific and Technological
Research Council (TUBITAK) and Hacettepe University
(HU) for the financial support of this work through Projects
TBAG-HD/249 and SAN-TEZ 00875-2011 (HU-Industry
Cooperation), respectively.
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