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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.
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
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
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.
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 %).
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.
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]
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