You are on page 1of 10

Nanoencapsulation of intercalated montmorillonite-urea within PVA

nanofibers: Hydrogel fertilizer nanocomposite


Mohammad Hossein Azarian,1,2 Wan Ahmad Kamil Mahmood ,1 Eunice Kwok,1
Wan Farahhanim Bt Wan Fathilah,1 Nor Fazilah Binti Ibrahim1
1
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden Penang, Malaysia
2
Department of Chemistry, Faculty of Science, King Mongkut’s University of Technology Thonburi,
Thungkru, Bangkok 10140, Thailand
Correspondence to: W. A. K. Mahmood (E - mail: wakcm@usm.my)

ABSTRACT: This study describes the preparation and characterization of nanofibers with poly(vinyl alcohol) (PVA) as the wall matrix
to encapsulate montmorillonite (MMT) clay and intercalated MMT-urea nanocomposite using an electrospinning technique. Nanofib-
ers encapsulated with (1–5%, w/w) MMT clay were successfully produced and characterized in relation to morphological, spectro-
scopic, structural, surface, and thermal properties. The electrospinning conditions for voltage, flow-rate, and emitter to collector
distance were 20 kV, 0.5, and 0.25 mL/h, and 10 cm, respectively. The surface roughness increased from 43.5 (empty fibers) to 56 nm
in the PVA/MMT-3% and bead-less nanofibers were formed with the maximum diameter distribution and mean diameter value of
45–80 and 62 nm, respectively. The d-spacing was increased significantly from 1.004 in MMT to 1.684 nm in MMT-urea, indicating
the intercalation of urea occurred successfully. Furthermore, elemental analysis results showed that the intercalated MMT-urea con-
tained 30.4% nitrogen. V C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45957.

KEYWORDS: clay; electrospinning; fibers; films

Received 21 June 2017; accepted 22 October 2017


DOI: 10.1002/app.45957

INTRODUCTION Water is one of the main concern that affect the production of
cultivation, therefore use of superabsorbent polymers as water
Nitrogen is one of the most essential elements in plants nutri-
management materials for agricultural applications is necessary.
tion and among the available commercial nitrogen source fertil-
Superabsorbent polymers have the characteristic of absorbing
izers, urea is widely used due to its lower production cost and
large amounts of water and make it available to the plants by
high nitrogen content. However, more than half of applied urea
gradually release their load into soil over a long period. PVA is
can be lost into the environment due to leaching, decomposi-
tion, and ammonium volatilization, make it not very efficient a superabsorbent biodegradable polymer hydrogel that is gener-
fertilizer.1,2 To overcome those challenges, intercalating of urea ally known as a safe substance due to its nontoxic properties
into montmorillonite (MMT) clay has the potential to reduce and its ability to absorb and retain large volumes of water.5,6
losses and increase the fertilizer efficiency. Furthermore, the PVA nanofiber will be used to improve water availability and
nanoencapsulation of MMT-urea within superabsorbent poly- also act as a host matrix of MMT-urea fertilizer. Lee et al.7 have
mer such as poly(vinyl alcohol) (PVA) can be used for water prepared PVA/MMT clay nanofiber mats by the electrospinning
retention. technique with an average diameter of 250 nm containing dif-
ferent amount of MMT contents (1–10 wt %) which results in
MMT is a natural 2:1 layered alumina silicate and most abun-
improvement in tensile strength and thermal stability of the
dant mineral which can be used to intercalate molecular species
nanocomposites. Han et al.8 prepared a biodegradable starch–
due to its excellent properties such as high cation exchange
PVA blend film to coat the granular fertilizer and found a sig-
capacity and environmental friendly nature.3 Pereira et al.4 have
nificant increase in water absorbency and NH4 permeability of
reported the preparation of slow release nanocomposite based
the coated film with increase the PVA wt % in the composite.
on urea intercalated MMT clay by an extrusion process and
showed urea contents ranging from 50 to 80 wt % has slow Electrospinning is a relatively cheap and efficient technique for
release behavior. the fabrication of polymer composite nanofibers.9 The one step

C 2017 Wiley Periodicals, Inc.


V

45957 (1 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

electrospinning process can be utilized for the production of a electrically grounded and rotated at 300 rpm placed at a con-
variety of polymer nanofibers by applying the high voltage to a stant distance of 10 cm to the capillary tip. The electrospinning
polymer solution.10,11 Urea-intercalated MMT can be incorpo- was performed at room temperature and all the web fiber films
rated into polymer solution for electrospinning to produce were collected on the aluminum foil.
composite nanofibers. Nanoencapsulation of urea-MMT clay
Materials Characterization
within PVA nanofiber reduces the spread of fertilizer in water
The morphology and surface structure of the composite nano-
and soil and minimizes the risk of hazardous in environments.
fibers were investigated using a scanning electron microscope
In this study, PVA/MMT and PVA/MMT-urea superabsorbent
(SEM; Quanta FEG 650 2012, FEI, Hillsboro, OR), transmission
nanofiber composite films were prepared using electrospinning
electron microscope (TEM; Zeiss Libra120, Carl Zeiss AG,
technique. Such materials were characterized regarding their
Oberkochen, Germany), and atomic force microscopy (AFM;
spectroscopic, structural, morphological, surface, and thermal
Dimension Edge, Bruker, Billerica, MA). Statistical image proc-
properties. The prepared nanofiber composite believed to effi-
essing was done on the SEM microimages by fiber separation
ciently improve the utilization of fertilizer and water resources
through Digimizer image analyzer. Consequently fiber diameter
simultaneously.
distribution was determined using software Minitab 17.2.0
EXPERIMENTAL DETAILS (Minitab Ltd., Coventry, UK) to obtain mean diameter and
Materials their respective histograms. The elemental analysis was deter-
PVA (MW 5 25,580 g/mol) and MMT clay K10 were purchased mined using a CHN Analyzer (Perkin Elmer II, Waltham, MA).
from Sigma Aldrich (St. Louis, MO) while urea was purchased Surface roughness was calculated through AFM nanoscope anal-
from GmbH chemicals (Homburg, Germany) and used without ysis version 1.40 (Bruker) software. X-ray diffraction (XRD)
further purification. Double-distilled water (DDW) was used as analysis (X’Pert MRD PANalytical, Almelo, the Netherlands)
the solvent. and Fourier transform infrared (Perkin Elmer System 2000
FTIR, Waltham, MA) were employed to study the structure of
Preparations of PVA Solutions and PVA/MMT Suspensions the PVA and its composition with MMT clay. For XRD, the dif-
To find out the best concentration of PVA in the solution, vari- fracted beam was detected over the range 2–808 (2u). Samples
ous amount of PVA powder was dissolved in DDW at 15, 18, for FTIR analysis were prepared by KBr pellet in the range
and 19.5% w/v. The solutions were heated up to 80 8C under 4000–400 cm21 at room temperature with 16 times scanning.
magnetic stirring for 15 h. PVA solution were then electrospun Thermal stability of nanofiber was tested using thermal gravi-
and it was found that 19.5 wt % PVA formed the most favor- metric analyzer (TGA/SDTA851, Mettler Toledo, Columbus,
able nanofibers film. PVA/MMT suspensions were prepared by OH) from ambient temperature to 900 8C at a heating rate of
dispersing MMT clay in DDW at three different concentrations 20 8C min21 under Nitrogen gas. Test samples (5 mg) were
(1, 3, and 5 wt %) under magnetic stirring for 24 h at ambient taken for measurements, where the weight losses of the sample
temperature. The suspensions were further sonicated for 3 h. against the change of temperature data were recorded. Differen-
PVA powder (19.5 wt %) was then added to the clay suspen- tial scanning calorimetry (DSC; Pyris 1 2000, Perkin Elmer)
sions and heated to 80 8C, followed by magnetic stirring for analysis of composite nanofibers were performed from ambient
15 h. After sonicating for 3 h, the suspensions were electrospun temperature to 275 8C at 10 8C min21 and held for 5 min and
by electrospinning machine. finally cooled down to ambient temperature at 100 8C min21.
Intercalation of Urea within MMT Layer RESULTS AND DISCUSSION
0.1 g of MMT clay was added to 10 mL of saturated urea solu-
XRD Study
tion and stirred for 1 h and further sonicated using an ultra-
The XRD fingerprints of MMT clay, MMT-urea, PVA nanofiber
sonic bath. The reaction mixture was transferred into round
film, and PVA/MMT nanocomposite films are shown in Figure
bottom flask and refluxed at 70 8C for 4 h constantly. The sus-
1. As shown in Figure 1(a), the peak at 2u 5 8.808
pension finally filtered by using a Buckner funnel and washed
(d 5 1.004 nm) can be attributed to the basal spacing of the
several times with DDW and kept into the desiccator. CHN ele-
MMT clay, while in Figure 1(b), the peak at 2u 5 19.48 and
mental analysis was done to determine the percentage of nitro-
other sharp peaks are attributed to the semi-crystalline structure
gen in the intercalated MMT clay samples. Based on the
of PVA nanofibers.12 With encapsulating of 1% MMT to PVA
analysis, the percentage of nitrogen for intercalated MMT-urea
in the PVA/MMT composite nanofibers, the intensity of the
was 30.4%.
broad peak at 19.48 of pristine PVA decreases [Figure 1(c)] and
Preparation of PVA/MMT Composite Nanofibers by further become plateau with 3% of MMT. These changes could
Electrospinning likely be attributed to the decreasing level of crystallinity after
The PVA/MMT and PVA/MMT-urea suspension were loaded in addition of MMT. Furthermore, the basal spacing of MMT clay
the 5 mL plastic syringe and placed into the syringe pump increase and split to 1.095 and 2.006 nm with 3% MMT load-
(SP1000, Fanavaran Nano-Meghyas, Tehran, Iran). A constant ing. This observation reveals the formation of intercalated struc-
high voltage electricity adjusts at 20 kV was then applied via an tures due to the expansion of MMT clay layers. Moreover, as
alligator clip attached to the syringe’s needle. The solution was shown in Figure 1(e) the basal spacing of clay split and diffrac-
pumped to the needle tip via a syringe controller with different tion angle shift to 2u 5 5.258 with the d spacing value of
feed rates of 0.25 and 0.5 mL/h. A drum collector which was 1.685 nm, which is resulting from the intercalation of urea

45957 (2 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

merely a physical entrapment rather than any sort of chemical


interaction. The spectrum of MMT-urea at Figure 2(e) shows
some changes in MMT structure due to the intercalation pro-
cess. The peak at 1645 cm21 (OH bending) of MMT clay shows
a blue shift and changed to 1601 cm21 in intercalated MMT-
urea nanocomposite. The new peaks also appeared at 1466,
1680, and 3339 cm21 which are due to the CAN, carbonyl
group and NAH stretching of urea, respectively. Therefore, we
can conclude that the intercalation of urea successfully occurred
between the interlayer of MMT clay structure. Moreover, the
spectrum of PVA/MMT-urea at Figure 2(f) shows the similar
characteristics of PVA/MMT-%3 spectrum except the broader
peak at 3380 cm21. Furthermore, CHN elemental analysis was
done to determine the percentage of nitrogen in the intercalated
MMT clay sample. Based on the analysis, the percentage of
nitrogen in MMT-urea was 30.40% which shows that the com-
posite contains significant amount of nitrogen.
SEM
Changing the polymer concentration could affect the fibers for-
mation in PVA as shown in Figure 3. Figure 3(a) shows that in
15 wt % PVA concentration, beaded electrospun fibers were
Figure 1. Fingerprint of (a) MMT clay, (b) PVA, (c) PVA/MMT-1%, (d) formed. Investigating of PVA in this concentration with two dif-
PVA/MMT-3%, (e) MMT-urea, and (f) PVA/MMT-urea. [Color figure ferent flow rates show that electrospinning at higher flow rate
can be viewed at wileyonlinelibrary.com] (0.5 mL/h) caused the formation of larger beads [Figure 3(a0 )].
Furthermore, the beaded electrospun fibers still formed after
within the clay layer structures. However, the basal spacing of increasing the concentration to 18 wt % and changing the flow
MMT merged and slightly decreased to 1.540 nm with the dif- rates have not much effect on the formation of beads [Figure
fraction angle of 5.738 in PVA/MMT-urea nanocomposite. The 3(b,b0 )]. The low polymer concentration can have caused the
same observation was reported by our group after encapsulation formation of beads in electrospun nanofibers which is mainly
of MMT clay within poly(ethylene glycol) nanoparticles by elec- due to surface tension dominance over viscoelastic forces,
trospraying technique.13 resulting in absence of chain entanglement between polymer
Infrared Spectroscopy (FTIR) and Elemental Analysis
Figure 2 shows the infrared spectra of PVA nanofiber, MMT
clay, PVA/MMT with different percentage of MMT clay and
MMT-urea nanocomposites. The spectrum of the neat PVA
fiber at Figure 2(a) shows the broad band at 3368 cm21 due to
the hydroxyl group. Furthermore, bands at 2894 and 2940 cm21
are due to vibration stretching of CH and CH2 groups and
bands at 1371 and 1431 cm21 are attributed to their deforma-
tion vibration. The band at 1736 cm21 is the characteristic peak
of the carbonyl group from the acetate groups of poly(vinyl ace-
tate) which remained in the PVA polymer. The spectrum of
MMT at Figure 2(b) shows some peaks related to its structure.
A broad peak at 3450 cm21 is related to the absorbed water
molecules and peaks at 1645 and 1040 cm21 are due to the OH
bending and SiAO stretching, respectively.14 The spectrum of
the PVA/MMT-1% nanocomposite is similar to spectrum of
pure PVA nanofiber. The feature of the spectrum does not
change from PVA/MMT-1% to the other PVA composite with
higher MMT contributions except for the band of hydroxyl
group which becomes broader in PVA/MMT-5% due to increas-
ing amount of MMT in the nanocomposite. From the FTIR
results we can clearly observe that, there is no any chemical
interaction between PVA and MMT clay as similarly observed Figure 2. FTIR spectra of (a) PVA nanofiber, (b) MMT clay, (c) PVA/
and reported by other researchers.15,16 Thus, we can finalize MMT-1%, (d) PVA/MMT-3%, (e) MMT-urea, and (f) PVA/MMT-urea.
that the encapsulation of MMT within the PVA nanofibers was [Color figure can be viewed at wileyonlinelibrary.com]

45957 (3 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 3. SEM micrograph of PVA nanofiber mats prepared by various conditions: (a) 15% and 0.25 mL/h, (a0 ) 15% and 0.5 mL/h, (b) 18% and
0 0
0.25 mL/h, (b ) 18% and 0.5 mL/h, (c) 19.5% and 0.25 mL/h, (c ) 19.5% and 0.5 mL/h.

89 nm in PVA 19.5% with flow rate of 0.5 mL/h to 67.7 nm in


molecules.17,18 In the case of PVA 19.5% with flow rate of
PVA 19.5% with the flow rate of 0.25 mL/h. These results sug-
0.25 mL/h, nanofibers have shown a uniform morphology and
gested that using 19.5% PVA total concentration with the flow
no beads formation was observed mainly due to significant
rate of 0.25 mL/h was ideal to produced optimal electrospun
increase of jet chain entanglement resulting in viscoelastic force
nanofibers with lower average diameter and thus was selected as
dominance over columbic repulsion.19 However, when the same
the suitable condition for encapsulating of MMT clay.
concentration of PVA used with higher flow rates (0.5 mL/h) as
shown in Figure 4(b) nanofibers partially coalesced and non- Figure 5 shows the PVA/MMT nanofibers including various
individualized fibers were observed. Furthermore, as illustrated quantities of MMT (1, 3, and 5%). The formation of beads and
in Figure 6(a), the average diameter decreased significantly from fiber’s diameter could be affected by the MMT concentration in

45957 (4 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 4. High magnification SEM images of PVA 19.5% with flow rate of (a) 0.25 and (b) 0.5 mL/h.

the solution. Fiber diameter versus MMT percentages are plot- disappeared and the maximum diameter distribution and the
ted as histograms and shown in Figure 6. The histogram of mean value slightly increased to 45–80 and 62 nm, respectively.
empty PVA nanofibers shows that the maximum diameter dis- In the PVA/MMT-5% [Figure 5(d)], the maximum diameter
tribution is in the range 45–85 nm with mean value of 67.7 nm. distribution and mean value decreased to 35–75 nm and 54 nm
The range decreased to 30–60 nm with mean value of 43 nm respectively and some small beads were observed in the scan
with loading of 1% MMT clay and few beads were observed. area. This is worth to mention that only in PVA/MMT-3% no
However, In the PVA/MMT-3% [Figure 5(c)], the beads are beads formation was observed. Figure 8 shows the PVA/MMT-

Figure 5. SEM micro images of PVA/MMT nanofibers prepared with MMT contents of (a) 0, (b) 1, (c) 3, and (d) 5 wt % (PVA solution concen-
tration 5 19.5% wt %).

45957 (5 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 6. Fiber diameter distribution of (a) PVA nanofiber with flow rate of 0.25 mL/h versus PVA nanofiber with flow rate of 0.5 mL/h, (b) PVA nano-
fiber versus PVA/MMT-1%, (c) PVA nanofiber versus PVA/MMT-3%, and (d) PVA nanofiber versus PVA/MMT-5%. [Color figure can be viewed at
wileyonlinelibrary.com]

Figure 7. TEM images of (a) PVA nanofiber, (b) PVA/MMT-3%, (c) MMT clay, and (d) intercalated MMT-urea.

45957 (6 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

Figure 8. SEM and TEM micro images of encapsulated PVA/MMT-urea composite nanofiber. [Color figure can be viewed at wileyonlinelibrary.
com]

Figure 9. (a,a0 ) 2D and 3D AFM topography images of PVA (19.5 wt %, flow rate 0.25), (b) 3D image of PVA/MMT-3%, and (c) 3D image of PVA/
MMT-5%. [Color figure can be viewed at wileyonlinelibrary.com]

45957 (7 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

Table I. Mean Roughness (Ra) and Root-Mean Square Roughness (Rq)


Determined from AFM Images for PVA Nanofiber Film and its Composi-
tion with MMT Clay

Polymer and composites Ra (nm) Rq (nm)


PVA 43.5 55
PVA/MMT-1% 47 59
PVA/MMT-3% 56 69.5
PVA/MMT-5% 45 58

urea nanofibers including 3% intercalated MMT-urea nanocom-


posite. The fibers are formed with no beads formation and no
difference was found in compare to PVA/MMT-3%.
TEM
The TEM micrographs of PVA, PVA/MMT-3% nanofibers,
MMT clay and intercalated MMT-urea are shown in Figure 7.
Figure 11. DTG curves of (a) PVA, (b) PVA/MMT-1%, (c) PVA/MMT-
The TEM microimage of PVA 19.5% at Figure 7(a) shows the 3%, (d) PVA/MMT-5%, and (e) PVA/MMT-urea. [Color figure can be
nanofibers without any beads formation. However, TEM obser- viewed at wileyonlinelibrary.com]
vation of PVA/MMT-3% at Figure 7(b) clearly indicates that the
presence of MMT clay in PVA caused the color of the nanofiber
Figure 9. Figure 9(a) and (a0 ) show the 2D and 3D images of
turned to darker. The diameter of the PVA and its composition
electrospun PVA nanofibers (19.5 wt %). An evaluation of PVA
with MMT clay is approximately 70–75 nm which is in a good
mats revealed the formation of nanofibers with random orienta-
agreement with SEM. The TEM microimages of MMT and tions. The neat PVA nanofiber prepared with no MMT content
intercalated MMT-urea at Figure 7(c,d) clearly indicate the obviously exhibits smoother surface with lowest surface rough-
changes of MMT color due to the urea intercalation process. As ness. The average roughness (Ra) of nanofiber mats increased
illustrated in Figure 8, intercalated MMT-urea was clearly from 43.5 to 47 nm and 56 nm after 1 and 3 wt % of MMT
observed within PVA nanofibers at higher magnifications in loading respectively (Table I). However, as the percentage of
PVA/MMT-urea 3%. TEM investigation clearly showed that the MMT was increased to 5 wt % the Ra decreases to 45 nm. This
encapsulation of MMT-urea occurred successfully and the mor- attributed to the better dispersion of MMT in its higher loading
phology of the PVA nanofibers did not change after encapsulat- content. From the 3D image of PVA/MMT-5% [Figure 9(c)], it
ing with MMT-urea clay. is evident that the beads in the fibers are appear at this MMT
AFM concentration. However, the formation of fibers showed more
AFM micro images of electrospun PVA nanofiber film and its smooth and smaller in diameter in compare to PVA/MMT-3%.
composition with different percentage of MMT are shown in Higher MMT content dispersed uniformly in PVA composites
results in fibers with lower diameter and smoother surface.
TGA
The thermal behavior of the prepared nanofiber composites was
characterized using TG-DTG methods. Figure 10(a) shows two
major weight loss stages for PVA nanofiber film. The first stage
of degradation (7.57% at 30–170 8C) is attributed to loss of
moisture and physically adsorbed water. The major stage of deg-
radation (92.4% at 170–909 8C) corresponds to decomposition
of PVA backbone. In the case of PVA/MMT-1% as shown in
Figure 10(b), three stage of degradation can be observed. The
major (70.25%) and third (21%) stage of decomposition were
occurred at 161–422 and 422–908 8C, respectively. This is due to
the protective effect of MMT clay which increases the thermal
stability of PVA portion. However, for the PVA/MMT-3%, PVA/
MMT-5%, and PVA/MMT-urea as shown in Figure 10(c–e), the
major degradation percentage increased and reached to 77% as
compared to PVA/MMT-1%, while their third degradation per-
centage decreased to 14% consequently. The maximum degrada-
Figure 10. TGA curves of (a) PVA, (b) PVA/MMT-1%, (c) PVA/MMT- tion temperatures (Tmax) of PVA at 334 8C, decreased to 328 8C
3%, (d) PVA/MMT-5%, and (e) PVA/MMT-urea. [Color figure can be with 1% addition of MMT clay. However, as shown in Figure 11,
viewed at wileyonlinelibrary.com] the Tmax shows further decrease in the composition of PVA/

45957 (8 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

nanofibers. On the other hand MMT acts as plasticizer which


decreases the glass transition temperature by increasing the dis-
tance between PVA polymer chains in the PVA/MMT nanocom-
posites.21,22 The DSC thermogram for PVA nanofiber shows the
exothermic peak with the value of 199.35 8C corresponds to the
Tm of the polymer backbone. With loading of 1% MMT clay
Tm of PVA polymer shows a slight negative shift (197.59 8C) in
PVA/MMT-1%. However, with higher loading of MMT clay Tm
shows a slight positive shift in temperature and reach to 197.66
and 198.10 8C in PVA/MMT-3% and PVA/MMT-5%, respec-
tively. Moreover, the Tm of PVA/MMT-urea shows a slight
decrease in compare to PVA/MMT-3%. A change of Tm of PVA
nanofibers after an addition of MMT clay is according to a
change between a semi-crystalline phase and amorphous phase
of polymer matrix.23 The degree of crystallinity (Xc) of PVA
and its composition with different MMT percentage was calcu-
lated from the formula suggested by Pielichowsk and Flejtuch.24
The heat required for melting of 100% crystalline PVA polymer
was 138.60 J g21.25 The degree of crystallinity of PVA and its
composition are presented in Table II. With 1, 3, and 5 wt % of
MMT the crystallinity of the PVA/MMT nanocomposites
Figure 12. DSC curves of (a) PVA nanofiber, (b) PVA/MMT-1%, (c) decreased to 19.59, 17.66, and 14.63%, respectively.
PVA/MMT-3%, (d) PVA/MMT-5%, and (e) PVA/MMT-urea. [Color fig-
CONCLUSIONS
ure can be viewed at wileyonlinelibrary.com]
The present study demonstrates and evaluates nanoencapsula-
MMT-3%, PVA/MMT-5%, and PVA/MMT-urea and reached to tion of MMT and intercalated MMT-urea nanocomposite within
320, 319, and 315 8C, respectively. The thermal behavior of the PVA nanofiber polymer matrix through electrospinning tech-
nanocomposite samples indicates that the higher loading of nique. PVA with 19.5% w/v concentration and its encapsulation
MMT clay can accelerate the thermal decomposition. This with 3% MMT and MMT-urea have shown an uniform fiber
decrease in the thermal stability of the nanocomposites is the morphology and no beads formation was observed. The data
consequence of the catalytic decomposition of MMT clay.20 obtained by FTIR, CHN, TEM analysis confirmed the presence
of urea within MMT clay layers and based on XRD analysis the
DSC basal spacing of MMT increased to 1.684 nm. The average
The DSC heating curves of the neat PVA nanofibers and the roughness (Ra) of PVA nanofiber mat increased in PVA/MMT-
PVA/MMT composite nanofibers with various MMT encapsula- 3%, but exhibited a lower glass transition and crystallinity. The
tion (1, 3, and 5 wt %) are shown in Figure 12. The DSC analy- FTIR spectrum of the PVA/MMT nanofibers are almost the
sis of PVA nanofiber as shown in Figure 12(a) revealed the same as those of the original samples, which indicates that there
presence of a glass transition temperature (Tg) and melting tem- was no chemical interaction between PVA and MMT clay. The
perature (Tm) with values of 81.45 and 199.35 8C, respectively. prepared fiber nanocomposites have the potential to be applied
The encapsulation of MMT clay to PVA nanofibers results in for slow-release fertilizer application. However, further investiga-
shift of Tg towards lower temperature, from 81.48 8C in the neat tion will be needed to explore the ability of the PVA/MMT-urea
PVA to 78.14 8C in the PVA/MMT-1%. This value further fertilizer in crop plants.
decrease to 54.93, 54.96, and 53.43 8C in the PVA/MMT-3%,
PVA/MMT-5%, and PVA/MMT-urea, respectively. The mobility ACKNOWLEDGMENTS
of the PVA macromolecular chains enhanced due to increasing M.H.A. gratefully acknowledges Universiti Sains Malaysia for
the free volume of polymer in the PVA/MMT composite financial support POST GRADUATE RESEARCH GRANT
SCHEME (PRGS: 1001.PKIMA.846015) and FUNDAMENTAL
Table II. DSC results of the PVA and PVA/MMT nanofiber composites
RESEARCH GRANT SCHEME (FRGS: 203.PKIMIA.6711421)
with various compositions of MMT clay
from Ministry of Education.

Sample Tg (8C) DHm (J g1) Xc (%) Tm (8C)


PVA 81.48 31.65 22.89 199.35 REFERENCES
PVA/MMT-1% 78.14 27.15 19.59 197.59
1. Edrisi, A.; Mansoori, Z.; Dabir, B. Int. J. Greenh. Gas Con-
PVA/MMT-3% 54.93 24.48 17.66 197.66
trol. 2016, 44, 42.
PVA/MMT-5% 54.96 20.28 14.63 198.10
2. Ibrahim, K. R. M.; Babadi, F. E.; Yunus, R. Particuology.
PVA/MMT-urea 53.43 24.17 17.43 197.18
2014, 17, 165.

45957 (9 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957


ARTICLE WILEYONLINELIBRARY.COM/APP

3. Paiva, L. B.; Morales, A. R.; Valenzuela Dıaz, F. R. Appl. 14. Kianfar, A. H.; Mahmood, W. A. K.; Dinari, M.; Azarian, M.
Clay Sci. 2008, 42, 8. H.; Khafri, F. Z. Spectrochim. Acta Part A: Mol. Biomol. Spec-
4. Pereira, E. I.; Minussi, F. B.; Cruz, C. C. T.; Bernardi, A. C. trosc. 2014, 127, 422.
C.; Ribeiro, C.; Luiz, R. W.; Luiz, R. W. J. Agric. Food Chem. 15. Tan, W. L.; Abu Bakar, M. J. Alloys Compd. 2013, 561, 40.
2012, 60, 5267. 16. Chieng, B.; Ibrahim, N.; Yunus, W.; Hussein, M. Polymers.
5. Zhao, J.; Sun, Z.; Shao, Z.; Xu, L. Fibers Polym. 2016, 17, 896. 2013, 6, 93.
6. Can, M. F.; Avdan, L.; Bedeloglu, A. C. Polym. Compos. 17. Li, D.; Xia, Y. Adv. Mater. 2004, 16, 1151.
2015, 36, 2334.
18. Wang, C.; Cheng, Y. W.; Hsu, C. H.; Chien, H. S.; Tsou, S.
7. Lee, H. W.; Karim, M. R.; Ji, H. M.; Choi, J. H.; Ghim, H. Y. J. Polym. Res. 2011, 18, 111.
D.; Park, S. M.; Oh, W.; Yeum, J. H. J. Appl. Polym. Sci.
2009, 113, 1860. 19. Hani, N. M.; Torkamani, A. E.; Azarian, M. H.; Mahmood,
K. W.; Ngalim, S. H. J. Sci. Food Agric. 2017, 97, 3348.
8. Han, X.; Chen, S.; Hu, X. Desalination. 2009, 240, 21.
20. Qin, H.; Su, Q.; Zhang, S.; Zhao, B.; Yang, M. Polymer.
9. Wang, S. H.; Sun, L. G.; Zhang, B.; Wang, C.; Li, Z. W.; He,
2003, 44, 7533.
J. Z.; Zhang, J.; Xie, Y. Polym. Compos. 2011, 32, 437.
21. Gao, W.; Dong, H.; Hou, H.; Zhang, H. Carbohydr. Polym.
10. Khan, W. S.; Asmatulu, R.; Ceylan, M.; Jabbarnia, A. Fibers
2012, 88, 321.
Polym. 2013, 14, 1235.
22. Pagacz, J.; Pielichowski, K. J. Therm. Anal. Calorim. 2013,
11. Itoh, H.; Li, Y.; Chan, K. H. K.; Kotaki, M. Polym. Bull.
111, 1571.
2016, 1.
12. Ricciardi, R.; Auriemma, F.; De Rosa, C.; Laupr^etre, F. Mac- 23. Yang, C. C.; Lee, Y. J. Thin Solid Films. 2009, 517, 4735.
romolecules. 2004, 37, 1921. 24. Pielichowski, K.; Flejtuch, K. Polym. Adv. Technol. 2002, 13,
13. Wan, A. K. M.; Azarian, M. H.; Wan, F. H.; Kwok, E. J. 690.
Appl. Polym. Sci. 2017, 134, 1. 25. Guirguis, O. W.; Moselhey, M. T. H. Nat. Sci. 2012, 04, 57.

45957 (10 of 10) J. APPL. POLYM. SCI. 2018, DOI: 10.1002/APP.45957

You might also like