Effect of Solution Concentration On The Electrospray/Electrospinning Transition and On The Crystalline Phase of PVDF
Effect of Solution Concentration On The Electrospray/Electrospinning Transition and On The Crystalline Phase of PVDF
Effect of Solution Concentration On The Electrospray/Electrospinning Transition and On The Crystalline Phase of PVDF
Received March 19th, 2010; revised June 17th, 2010; accepted June 21st, 2010.
ABSTRACT
A study was conducted regarding the effect of concentration of poly (vinylidene fluoride) (PVDF)/N,N-dimethylformamide
(DMF) and PVDF/DMF/acetone solutions on the transition between electrospray and electrospinning and on the for-
mation of the and crystalline phases of PVDF. The crystalline phases present in the samples, crystallinity and
morphology were determined by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry
(DSC) and scanning electron microscopy (SEM), respectively. Low concentration solutions resulted in films consisting
of small droplets (electrospray) containing predominantly the phase. High concentration solutions resulted in a
non-woven mesh of nano-to-micron diameter fibers (electrospinning) containing exclusively the phase. These results
showed that, the formation of this phase in the electrospinning is related mainly to the solvent evaporation rate, and not
to drawing experienced by the polymer during the process. Solvent type affected the amount of crystalline phase present,
the boundary concentration between the two processes and the average diameter of fibers. Meshes processed by elec-
trospinning display a degree of crystallinity higher than the films obtained by electrospray.
Keywords: Poly(Vinylidene Fluoride) (PVDF), Electrospinning, Electrospray, Crystalline Phase, Fibers, Morphology
perienced by the polymer jet solution. This elongation Table 1. Properties of the solvents used (20℃).
process would be similar to the well known transi- Boiling
Density Viscosity
tion caused by mechanical drawing at T 90℃ [2-6]. Solvent Formula
(g/mL) point (℃) (mPa.s)
A variant of electrospinning is electrospray [19]. The
Acetone C3H6O 0.786 56.5 0.326
basic difference between these two processes lies in the
concentration of the solution. In electrospray the concen- DMF C3H7NO 0.944 153 0.820
tration is sufficiently low to destabilize the charged jet
which then breaks down into small spherical droplets that
solidify during the course and are deposited on the col-
lector. In this case the polymer solution does not experi-
ence severe drawing and the formed film consists of
small droplets instead of fibers.
The objectives of the current investigation were: 1)
determine the solution concentration at which the transi-
tion between electrospray and electrospinning of PVDF
occurs and 2) verify through the electrospray technique,
where no stretching occurs, that the formation of the
phase depends fundamentally on the solvent evaporation
rate. The effect of the type of solvent in the process was Figure 1. Scheme of the setup used in the Electrospinning/
also verified. Electrospray process.
2. Experimental Methods
brated with In, using samples of 8 mg and heating rate
2.1. Materials of 10℃/min. Degree of crystallinity was determined by
The PVDF used was Foraflon® 4000HD, from Elf Ato- comparing the enthalpy of fusion of the sample obtained
chem. The solvents used were N,N-dimethylformamide by DSC with that of 100% crystalline PVDF- (104.5 J/g)
(DMF, Merck 99.5%) and acetone (Merck, 99.7%). So- [20]. Sample surface morphology was observed by using
lutions were prepared at concentrations of 5, 7, 10 and 15 a scanning electron microscope (Philips 30 FEG Model
wt% PVDF using as solvent pure DMF and a 3:1 v/v XL, operating at 15 kV) after gold coating. Size distribu-
mixture of DMF with acetone. The ratio of mixture DMF tion of the fibers diameters was determined by the soft-
and acetone was selected because they produce thinner ware “image J” developed by the National Institute of
and more homogeneous nanofibers in the electrospinning Health.
process [13]. Solubilization was carried out at 70℃ un- 3. Results and Discussions
der stirring for one hour. Table 1 shows some properties
of the solvents used. The micrographs in Figures 2(a) to (d) and 3(a) to (d)
present the morphology of the samples processed with
2.2. Electrospray/Electrospinning PVDF/DMF and PVDF/DMF/acetone solutions at dif-
A scheme of the system used in the electrospray/electro- ferent concentrations, respectively.
spinning process is shown in Figure 1. A 20-mL glass One can observe in Figures 2(a)-(b) (5 and 7 wt% in
syringe was used with a steel needle with internal di- DMF) and 3(a) (5 wt% in DMF/acetone) the formation
ameter of 0.7 mm. The distance between needle and col- of a film consisting of small droplets, characteristic of
lector was 3 cm and the electric voltage applied was 10 the electrospray process. The morphology of this film
kV, using a Bertan 210 30R (0-30 kV) high voltage source. depends among other things on droplet volume at impact
The collector used was an aluminum disk with diameter and on evaporation rate of the solvent [21]. In Figures
of 15 cm and width of 5 cm, at an angular velocity of 60 2(c)-(d) (10, 15 wt% in DMF) and 3(b)-(d) (7, 10 and 15
rpm. The process was carried out at 25℃ and RH 55%. wt% in DMF/acetone) fibers predominate, characteristic
of electrospinning. In micrographs 2(c) (10 wt% in DMF)
2.3. Characterizations and 3(b) (7 wt% in DMF/acetone) the electrospun sheets
The crystalline phases present in the samples were char- present some small droplets, demonstrating that concen-
acterized by transmission infrared spectroscopy (FTIR, tration was not yet ideal for the formation of homogene-
Perkin Elmer Spectrum 1000) in the range between 400 ous fibers. These results show that the boundary concen-
and 1000 cm-1 and with resolution of 2 cm-1. Calorimetric tration between electrospray and electrospinning ranges
analyses were conducted in a Perkin Elmer DSC-7, cali- from 7 to10 wt% PVDF in DMF and from 5 to 7 wt% in
(a) (b)
(c) (d)
(a) (b)
(c) (d)
Table 2. Melting point (Tm), enthalpy of fusion (H) and degree of cristallinity (%C) of the samples processed with
PVDF/DMF and PVDF/DMF/acetone solutions at different concentrations.
not related to drawing experienced by the polymer during Oriented Poly(Vinylidene Fluoride) Films Exclusively in
the process, as suggested by some authors. Formation of the Phase,” Journal of Polymer Science Part B: Poly-
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