Materials Today Communications 14 (2018) 1–9

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Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

The influence of electrospinning parameters and solvent selection on the T

morphology and diameter of polyimide nanofibers
⁎
Juliana Lasprilla-Boteroa, Mónica Álvarez-Láineza, , J.M. Lagaronb
a
Design Engineering Research Group–GRID, Product Design Engineering Department, Universidad EAFIT, Carrera 49 No 7sur-50, Medellín, Colombia
b
Novel Materials and Nanotechnology Group, IATA-CSIC, Calle Catedrático Agustín Escardino Benlloch 7, 46980 Paterna, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Polyimide (PI) fibers display excellent thermal and mechanical performance; they have been recently in-
Electrospinning vestigated to fabricate hydrophobic membranes (mats) for high-performance applications. We studied the effect
Solvent system of electrospinning processing parameters and solvent selection on the morphology and the diameter of PI fibers.
Solubility-electrospinnability map 11 different solvents and 22 solvent systems able to dissolve PI were located in a Teas graph with the aim of
Polyimide
building the solubility-electrospinnability map for this material. PI solutions prepared with various solvents were
Hydrophobicity
electrospun at different electrospinning process parameters according to a 34–1 fractional factorial design of
experiments. Polymer concentration and applied voltage were the most significant factors to create thin and
uniform fibers. More homogeneous fibers and reproducible electrospinning process were obtained by using
polymer concentrations above 15 wt%. However, all solutions showed different morphological evolution ac-
cording to the solvents used. Based on the solubility–spinnability region settled for this PI, non-woven mats were
obtained with rough surface fiber morphology and high water contact angle, suitable for applications such as
hydrophobic membranes for oil-water separation.

1. Introduction parameters on the diameter of nanofibers obtained from polymers such

Nanometric fibrous structures exhibit several advantages over the
conventional fibrous structures including high surface area to volume
ratio, versatile surface morphology, tailorable porosity and enhanced
mechanical performance. Hence they have become a research priority
for many industries interested in tissue engineering, filtration, drug
delivery, energy storage, sensors, smart dressing, oil-water separation
or hydrophobic surfaces [1–3]. Electrospinning is the most promising
method to create continuous and reproducible nanofibers. However,
electrospinning process involves, at the same time, several variables
related to each other, being time-consuming to find a set of process
conditions that work for specific polymer/solvent systems.
Several studies have concluded that polymer concentration and
applied voltage are the most significant factors affecting the nanofiber
morphology [1,4–11]. Thus, process parameters selection continues
being carried out on a trial-and-error basis, where an interaction be-
tween variables could be ignored and low efficiency in optimization is
induced [5]. These limitations can be avoided using Statistical Design of
Experiments (DoE) and statistical tools like regression analysis, re-
sponse surface methodology (RSM) and analysis of variance (ANOVA).
Several authors have studied the effects of electrospinning process
as Polyacrylonitrile [1,6,12], Polyvinylidene fluoride [4], Poly(styrene-
co-acrylonitrile) [5], Polyethyleneoxide [7], Bombyx Mori silk [8], Poly
(vinyl alcohol) [9,10], and Poly(3-hydroxybutyrate) [11] using DoE
and the above mentioned statistical tools. DoE also helps to examine the
individual and mixed effects of factors on a complex system, mini-
mizing the number of experiments as possible [4,7].
Regarding polymer concentration, there are two aspects to keep in
mind in polymer-solvent interactions. One of them refers to polymer
content in the solution. For high concentrations, there are more chain
entanglements and the charged jet begins to be stabilized producing
fiber-like structures; the higher the polymer concentration the thicker
the fiber cross-section [1]. For low concentrations, the entanglement
network is not so strong to stabilize the charged jet producing Rayleigh
(axisymmetric) instabilities and generating drops and fibers with beads
[13]. The second aspect has to do with solvent solubility and its in-
trinsic viscosity [14]. High solubility forms strong polymer-solvent in-
teractions making polymer chains swell and expand. Poor solubility
increases the polymer–polymer interactions promoting the polymer
chains contraction [15].
For the applied voltage, the Coulombic forces, at low voltage values
are not so high to overcome the surface tension of the polymer solution,

⁎
Corresponding author.
E-mail address: malvar26@eafit.edu.co (M. Álvarez-Láinez).

https://doi.org/10.1016/j.mtcomm.2017.12.003
Received 27 November 2017; Accepted 6 December 2017
Available online 07 December 2017
2352-4928/ © 2017 Elsevier Ltd. All rights reserved.
J. Lasprilla-Botero et al.
which produces solvent spray resulting in droplets and beads. As vol-
tage increases, the surface tension and viscoelastic forces begin to be
well-balanced allowing the formation of a straight and stable charged
jet that produces a narrow fibers diameter distribution. If the applied
voltage keeps increasing, the Coulombic forces overcome the viscoe-
lastic forces, breaking the charged jet during its flight, leading bigger
but irregular fibers [16].
As a consequence, to select a suitable solvent not only influences the
solution viscosity or electrical conductivity, but also affects diameter,
crystallinity, tensile strength and surface morphology of the electrospun
fibers [14]. Therefore, it is crucial to understand the properties of sol-
vents and non-solvents in the polymer-solvent interactions with the aim
of optimizing the electrospinning process conditions.
The term electrospinnability has been established to qualify the
polymer solutions to be electrospun for getting homogenous micron,
submicron or nanofibers [2]. However, this property does not describe
the solvent ability to solubilize the polymer, and does not allow to
determine whether a solvent of high solubility will produce a good
solution for electrospinning. Hence, to choose solvents for electro-
spinning is desirable to develop tools such as a solubility-electro-
spinnability map from a Teas graph, based on the theory that the se-
lected binary solvent system should dissolve the polymer and the
solubility parameter of the combined solvent should be closer to the
solvent that dissolve the polymer to allow the fiber formation [17]
Through the use of an electrospinnability–solubility map based on a
Teas graphs, some authors have analyzed the effect of the solvent on the
solubility and electrospinnability of various polymers such as:
Polycaprolactone [14], Polyethylene (terephthalate) [15] and, Poly-
methylsilsesquioxane (PMSQ) [17] using a single figure. Compared to
other 2D and 3D diagrams such as Crowley’s and Hansen’s graphs. Teas
diagram has all three solubility parameters presented onto a 2D trian-
gular map, without clustering the solvents into a three-dimensional
representation, allowing a more straightforward analysis of the polymer
solubility [14,17].
Ternary solubility diagram or Teas graph introduces the fractional
cohesion parameters mathematically derived from dispersion, polar and
hydrogen-bonding force components of the Hansen solubility para-
meters, in a 0–100 scaled triangular diagram. So, any solvent or
polymer with defined Hansen parameters can be located by plotting its
three fractional parameters [14,15,17].
Polyimides (PIs) are a high-performance engineering polymer with
macromolecular repeating units containing the functional imide group.
PIs are classified into aliphatic, semi-aromatic and aromatic. However,
the aromatic PIs are the most important due to their superior thermal
stability, high mechanical properties (e.g., low creep and high strength)
and good chemical resistance caused by the heterocyclic imide rings
and aromatic benzene rings in their macromolecular backbones. They
have found extensive uses as fibers, gas separation membranes, filters,
coatings, adhesives and composites for many years [18].
For the synthetic fiber industry, aromatic PIs represent an excellent
class of polymers due to its remarkable properties. Recent research
advances on aromatic PI fibers has been focused on the fabrication of
fibers at nano-scale range through techniques like electrospinning [19].
Electrospun aromatic PI nanofibers have demonstrated better me-
chanical properties (e.g., strength and modulus) than those made of
other high-performance polymers, such as PAN, Nylon, Nomex and PLA
[18,20–22] and also, they have been used to create smart textiles, self-
cleaning materials [19,23], particle filters [24,25], hydrophobic ad-
hesives [26] and membranes for oil-water separation [27,28].
Electrospun aromatic PI nanofibers are typically prepared via a two-
step method that includes: (1) to electrospin polyamic acid (PAA) (PI
precursor) nanofibers from its solution, and (2) to convert PAA nano-
fibers to PI nanofibers by thermal imidization at high temperatures
[18,28]. Another way to obtain electrospun aromatic PI nanofibers is by
using a soluble PI, where the polymer is solubilized in an organic sol-
vent and then, its solution is directly electrospun.
2
Materials Today Communications 14 (2018) 1–9
P84 is the brand name for a commercial soluble polymer of the
aromatic polyimide BTDA-TDI/MDI. This PI is insoluble in common
solvents, but it has been electrospun in a few organic solvent systems
(i.e. DMAC, DMF and DMSO) for a broad range of filtration applications
[24,25,29–32]. However, a comprehensive study of its electrospinning
process conditions, including the solvent selection, has not been per-
formed yet. In this work, we establish the effects of some electrospin-
ning process parameters on the morphology evolution and the average
fiber diameter with the contact angle of aromatic PI nanofibers. PI so-
lutions were made with various solvents and electrospun at different
process conditions according to an experimental procedure developed
using DoE. Results were analyzed by ANOVA and polynomial regres-
sion. Based on this, it was created an electrospinnability−solubility
map derived from a Teas graph.
To the best of our knowledge [24,25,29–32], this is the first time
that the solubility behavior of a commercial soluble grade aromatic PI
and its electrospinnability are correlated in a single map. Using this
map, solvents with different volatilities and conductivities were com-
bined and this effect on the nanofibers morphology and the transition
from beads to homogenous defect free fibers were analyzed. With these
solvent mixtures, it was possible to control the surface properties of
electrospun mats to be used as membranes, to obtain a higher water
contact angle for specific applications, such as hydrophobic surfaces for
oil water separation.
2. Experimental
2.1. Materials
The aromatic polyimide (PI) used in this work is P84 a powder
solution grade purchased from HP Polymer GmbH (Lenzing, Austria).
This is a fully imidized co-polyimide containing approximately 20% of
methyl phenylenediamine and 80% of toluene diamine (BTDA-TDI/
MDI). Its glass transition temperature is 315 °C, no melting point and
decomposition temperature over 550 °C. Dimethyl Sulfoxide (DMSO),
purchased from Carlo Erba Reagents (Italy), N, N-Dimethylformamide
(DMF), purchased from Panreac (Spain), N,N-Dimethylacetamide
(DMAC), N-Methyl-2-pyrrolidone (NMP), Ethanol, Chloroform,
Dichlorometane, Tetrachloroethane, Cyclohexanone and
Tetrahydrofuran purchased from Merck KGaA (Germany) were used as
received without further purification. All solvents were 99.9% pure.
2.2. Mapping solubility region of aromatic PI on a teas graph
The solubility behavior of this aromatic PI was evaluated in 11
solvents (including water) and 22 solvent mixtures, and tested at 10 wt
% of polymer concentration, at atmospheric pressure (85.11 kPa) and
room temperature of (296 ± 2 K). The polymer was added to the
solvent and magnetically stirred for less than 10 min and then, the
degree of dissolution or swelling of the polymer was visually assessed.
PI solubility was categorized and recorded as high, partial to high, and
poor based on the time taken to dissolve the polymer. Solvents and their
mixtures were located on a Teas solubility graph according to their
respective fractional solubility parameters [33] and categorized by
their solubility results, highlighting their positions using a color code.
2.3. Design of experiments (DoE)
DoE methodology was employed to identify and rank the effects of
four of the main factors of the electrospinning process on the fibers
diameter: polymer concentration (wt%), needle-tip to collector distance
(cm), voltage (kV) and flow rate (mL/h). It was selected a 34–1 frac-
tional factorial experimental design, which provided 27 randomized
experimental runs for the four evaluated factors. Each factor was varied
at three levels as described in Table 1. These values were determined
through previous studies carried out to form continuous fibers.
J. Lasprilla-Botero et al. Materials Today Communications 14 (2018) 1–9

Table 1 stainless steel needle (0.603 mm nominal ID – 20G with blunt tip), a
The experimental space explored. high voltage DC supply model EQ-30P1 (Matsusada Precision Inc,
Kusatsu) and an aluminum flat collecting screen (21 cm × 21 cm)
Factor Unit Level
wrapped with aluminum foil. All solutions were electrospun at room
Low (-1) Center (0) High temperature (296 ± 2 K) and stable relative humidity (56 ± 1%).
(+1) The morphology of electrospun PI fibers was observed using a field
emission scanning electron microscope (FE-SEM) model Schottky JSM-
PI concentration (A)* % PI wt/ 10 15 20
solvent wt 7100F (JEOL Ltd). Samples were coated with gold before being ob-
Needle tip-collector distance cm 7 10 13 served. Two images at X10000 of magnification were obtained from
(B)* each sample, being analyzed using Image J software. The average fiber
Voltage (C)* kV 6 8 10 diameter and its corresponding standard error were determined by
Flow rate (D)* mL/h 0.3 0.7 10
measuring 100 fibers chosen randomly. For fibers without defects and
*The bold letters in parenthesis are the factoŕs name, as it appears in the graphs. processing troubles, the electrospinnability region was identified. These
results were combined with the solubility results on the Teas graph to
A multivariable regression analysis and Daniel Plots were used to create the electrospinnability–solubility contour map.
identify the statistically most significant factors and interactions for
getting homogenous nanofibers. Both analyses were carried out em- 2.5. Wettability of electrospun PI membranes
ploying R–project software, and it was obtained the mathematical
models for the average fiber diameter of the electrospun PI fibers pro- The wettability of electrospun membranes was evaluated by static
duced with each solvent, and its corresponding ANOVA and regression water contact angle (WCA) measurements using a manual optical ten-
coefficients (R2) are presented. siometer (Theta lite TL 101, One Attension − Biolin Scientific) and 5 μL
drops of deionized water. The contact angle of each drop was measured
2.4. PI solutions characterization and electrospun fiber morphology after the drop has rested for 5 s on the PI membrane. All measurements
were performed in open air at ambient conditions (294.15 K and 60 RH
With solvents that dissolve the aromatic PI, it was prepared dis- %) and they were taken at five different places on the same sample.
solutions with different polymer contents (10, 15, and 20 wt%) in glass
flasks using magnetic stirring at 360 rpm for 2 h (at room conditions). 3. Results and discussion
The vials were sealed during the agitation time. Once dissolutions were
homogeneous, they were used for electrospinning. 3.1. Effect of solution characteristics on morphology and fiber diameter
Electrical conductivity and viscosity of PI solutions were measured
at room temperature (296.15 ± 2 K). Electrical conductivity was The best solvents for PI involved in our study were NMP, DMAC,
measured using an electrical conductivity meter (PC700, Oakton). The DMF, and DMSO, because the solubility parameters of these solvents
reported electrical conductivity value for each solution was the average are closest to PI (28.01 MPa1/2) (see Table 2), which indicates that their
of two measurements. Viscosity was evaluated under shear deformation molecular attraction forces are similar and allow the solvent molecules
using a rotational rheometer (Discovery Hybrid Rheometer, TA overcome the intermolecular forces in the polymer to produce the
Instruments). All samples were analyzed employing the parallel plates dissolution.
geometry, which consisted of a Peltier plate with plane circular geo- Fig. 1 shows the results obtained for different PI concentrations
metry and an environmental case attached to prevent solution drying. according to our DoE experimental runs. It can be observed the tran-
Flow sweeps were carried out at 298.15 K in a shear rate range from sition from beads to fiber morphology for each one of the solvents
0.1 s−1 to 1000 s−1. The specific viscosity value for each solution was tested; the resultant morphology evolution is attributed to the polymer
calculated using the Eq. (1) [34]: content and also to the electrical conductivity of the solution. For a
higher polymer content, fibers are defect free, because there are more
η0 − ηs
ηsp = polymer chain entanglements and less chain mobility hardening the jet
s (1)
extension, which reduce the disruptions during the electrospinning
Wherein ηsp is the specific viscosity, η0 is the zero shear rate viscosity, process, favoring the formation of large-diameter fibers [1,35]. How-
and ηs is the viscosity of the solvent used to prepare the polymer dis- ever, this analysis underestimates the role of the solvent −the media
solution. where the polymer molecules are moving- during the fiber formation
The electrospinning setup used was a horizontal array with a con- process.
trolled flow syringe pump (Cole Parmer), a 10 mL glass syringe with a All solutions have different morphology evolution according to the

Table 2
PI solubility, solution electrospinnability and solvent properties based on Smallwood 1996 and fractional solubility parameters based on Hansen 2007. Tb: Boiling temperature, Pv: Vapor
pressure at 25 °C, σ: Electric conductivity, η: Absolute viscosity, fd: Dispersion cohesion fractional solubility parameter, fp: Polar cohesion fractional solubility parameter, and fh: Hydrogen
bonding cohesion fractional solubility parameter.

Solvent Tb (K) Pv (kPa) σ (μs/m) η (mPa*s) δ (MPa1/2) PI solubility Electrospinnability 100 fd 100 fp 100 fh

NMP 475.15 0.06 2.00 1.80 23.0 High Spins 48.0 32.8 19.2
DMAC 439.15 0.16 0.10 0.92 22.8 Partial to high Spins 43.6 29.9 26.5
DMF 426.15 0.50 6.00 0.82 24.9 Partial to high Spins 41.0 32.3 26.7
DMSO 462.15 0.08 0.20 2.00 26.7 Partial to high Spins (beaded fibers) 40.9 36.4 22.7
Ethanol 351.15 7.86 0.14 1.08 26.5 Poor – 35.9 20.0 44.1
Chloroform 334.15 26.22 0.01 0.57 18.9 Poor – 66.9 11.7 21.4
Dichloromethane 313.15 58.10 4.30E-03 0.44 20.2 Insoluble – 59.5 20.6 19.9
Tetrachloroethane 419.15 0.58 250.00 1.58 21.6 Insoluble – 56.5 15.3 28.2
Cyclohexanone 429.15 0.62 5.00E-10 2.20 19.6 Insoluble – 60.9 21.6 17.5
Tetrahydrofuran 339.15 21.62 4.50E-03 0.55 26.7 Insoluble – 47.6 37.6 14.8
Water 373.15 3.16 100.00 0.89 47.8 Insoluble – 21.0 21.7 57.3

3
J. Lasprilla-Botero et al.
solvents used. NMP and DMAC solutions exhibit a smooth transition to
homogenous fibers, but in the case of DMF and DMSO the transition
occurs suddenly from beads to fibers. This difference in morphology
evolution is because of NMP and DMAC disclose a lower solubility
difference and electrical conductivity with PI, contrary to DMF and
DMSO. When the electrical conductivity of the polymer solutions in-
creases, the transition from beads to defect-free fibers occur earlier. PI
solutions made with DMSO have higher electrical conductivities values
than solutions made with NMP. An increase in the electrical con-
ductivity promotes the mobility of the electrical charges through the
fluid, making the fluid harder and moving forward the onset of the
lateral bending instability in the jet, which favors the formation of
bead-free uniform and thinner fibers [2,36].
Regarding the viscosity of solutions, in Fig. 2 (on the left side) it is
observed the increment in the specific viscosity with the increase of the
polymer content. When the polymer concentration increases, polymeric
chains reduce its mobility in the solution due to the chain entanglement
formation, which prevents the chain re-ordering and raises the solu-
tions viscosity [37]. Besides, two notable changes in the slope for PI
solution viscosities can be identified. These slope changes demark the
onset of semi-dilute unentangled, semi-dilute entangled, and
4
Materials Today Communications 14 (2018) 1–9
Fig. 1. Comparative plot of the average fiber dia-
meter, electrical conductivity and morphology evo-
lution results achieved with each one of the eval-
uated PI/solvent systems at 8 kV, 13 cm and 1 mL/h.
concentrated regimes [38].
The first slope change, as the polymer concentration increases from
7.5 to 10 wt% (or 12.5 wt% in the case of DMAC), is the entanglement
concentration (Ce), which marks the transition from semi-dilute un-
entangled to semi-dilute entangled regimes. Here, polymeric chains
start to overlap and form constrain entanglements [3]. Above Ce, the
level of macromolecular entanglement become very suitable for elec-
trospinning allowing a better stability of the charged jet, which pro-
duces uniform and regular electrospun fibers with large diameters
[2,3]. This behavior is observed in the mats with 10 and 15 wt% of PI,
whose micrographs are on the right side of Fig. 2.
The second slope change, from 12.5 to 15 wt%, occurs in a so called
C** concentration, which marks the beginning of the concentrated re-
gime where bead free fibers and globular fibers with macro beads can
be obtained. This is a result of the better cohesion between the polymer
chains in the solution, and its stronger macromolecular arrangement
[39]. For concentrations above 15 wt% defect-free electrospun nanofi-
bers were obtained with all solvents.
Wannatong et al. [16] proved that a significant difference between
the solubility parameter values of the polymer and the solvent induces
retraction of polymer molecules and generates a weak interaction
Fig. 2. Graphic correlation between specific
viscosity and PI content with morphology
evolution (left) and the fiber morphology
evolution by SEM (right).
J. Lasprilla-Botero et al.
Fig. 3. Daniel Plots with statistical analysis for average fiber diameters results. A: PI concentration, B: Distance needle-to collector, C: voltage and D: flow rate.
between polymer and solvent molecules, which may produce fibers
with beads [16]. Our results support this hypothesis, since solutions
made with DMAC and NMP, with solubility parameters more distant
from PI values, produced more beaded-fiber morphologies than those
made with DMF and DMSO. In fact, Ce and C** values from DMAC and
NMP solutions are higher than those of DMF and DMSO solutions.
On the other hand, the fiber diameter also increases directly with
solvents viscosity. Fibers produced from DMSO show the highest
average fiber diameter, while for fibers from DMF it is the lowest. The
solvents viscosity and the polymer-solvent physicochemical interac-
tions determine the final viscosity of the polymer solution [40]. When
the viscosity of the solution increases the beads becomes bigger; the
distance between them is longer, and its shape changes from spherical
to spindle-like; as a result the overall fiber diameter of the electrospun
fibers increases as well [41,42].
3.2. Effects of processing conditions on average fiber diameter
Fig. 3 displays the Daniel plots with the effects of the most sig-
nificant factors and their interactions, the p-values, and the regression
coefficients of the statistical-mathematical models for the average fiber
diameter. In these plots, points represent the estimated effect of each
factor and their interactions; if the point is far away from the line, this is
considered an important factor. The most significant factors are not the
same for all solvents; however, the polymer concentration (factor A)
and the applied voltage (factor C) have always the predominant effects
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Materials Today Communications 14 (2018) 1–9
(bigger estimates). These results mean that the formation of a uniform
fiber diameter depends mainly on these factors and not on the solvent
used to prepare the solution.
In the same way, the interaction between needle to collector dis-
tance (factor B) and the voltage (factor C) also have a significant effect.
This interaction is the electric field that affects the stretching and
drying processes of the jet. It is expected that a higher electric field
produces fibers with small diameters, but not all the solvents follow this
tendency. It is noted an influence of the volatility and viscosity of the
solvents. When the electric field is increased during the electrospinning
process, the charged jet travels much faster to the collector. Therefore,
the solvent in the jet has less time to evaporate and also, if the solvent
has lower vapor pressure (DMSO and NMP), wet fibers will be produced
with larger diameters [16].
For all models, regression coefficients (R2) are above 0.88, and
factors p-values and their interactions are below of the significance
level of 0.05, validating the sufficiency of these models to explain at
least 88% of the variability in the average fiber diameter.
3.3. Solubility and solution electrospinnability
Selecting suitable solvents for electrospinning is a complicated task.
Solvent properties are more than dissolving a polymer; moreover, they
are responsible for the fibers morphology. For solutions prepared at
15 wt% of PI, with selected solvents and designing effective solvent
systems, we combined the solubility and electrospinnability results to
J. Lasprilla-Botero et al.
Fig. 4. Solubility-electrospinnability contour map based on the ternary fractional parameter solubility diagram tested on solubility of aromatic PI at 15 wt% of polymer content,
85.11 kPa of atmospheric pressure and room temperature of 296.15 K. Success solutions zone are enlarged on the right size triangle. Red zone for high solubility area, green zone for
partial to high solubility area and dots represent the binary solvents systems. The apexes of each triangle denote the dispersion (100fd), the polar (100fp) and the Hydrogen bonding
(100fh) cohesion fractional solubility parameters. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
create a solubility-electrospinnability contour map (see Fig. 4). In this
contour map, they are used different colors to identify the solubility
capacity of each solvent and solubility–electrospinnability region is
enlarged on the right side of the picture. The Red zone is a very well
dissolved area, where it is obtained defect-free fibers without proces-
sing problems. In the green zone, the polymer is also well dissolved, but
during the electrospinning process the tip of the needle is partially
clogged, hindering the fiber formation and producing fibers with some
amount of beads. These problems were because the solvent evaporation
in the solution occurred so fast than the drop get dryer and did not
deform to create the charged jet [43].
This solubility–electrospinnability map provides useful guidance for
the solubility and electrospinnability of binary solvent systems for this
aromatic PI. Based on this graph, a solvent with high PI solubility (i.e
NMP) and solvents with partial PI solubility (i.e. DMSO) were mixed in
different ratios. For these mixtures, their positions in the electro-
spinnability–solubility map were calculated using the fractional solu-
bility parameters of each one of the solvent components following the
lever rule and the method proposed by Luo and coworkers [17] (black
dots in Fig. 4). According to this map, PI fibers were systematically
produced with several solvents and binary solvent systems. Fig. 5 shows
the fibers obtained with some mixtures tested, and their corresponding
average diameter (AD letters marked in yellow). It is observed that the
fiber diameters increase with raising density and boiling point of the
solvents. Fibers obtained with DMAC and DMSO mixtures showed the
highest diameters.
On the other hand, DMSO:DMF and DMAC:DMF solutions show
poor electrospinnability. This behavior is caused by the high volatility
of DMF compare to the other two solvents and the difference between
solubility parameters values of the polymer and the solvent mixtures.
Both factors produced clogged needle and interrupted the electrospin-
ning process continuity.
3.4. Hydrophobic behavior of PI mats (membranes)
It is also identified that physical properties of the solvents play a
significant role in the fiber surface morphology. It is perceived that
differences between volatility rates and conductivities might induce a
6
Materials Today Communications 14 (2018) 1–9
phase separation process during the fiber formation, which created a
rough surface morphology on the fibers.
In Fig. 6, it is presented fibers obtained from two different solvents
system. On the left, PI dissolves in NMP disclose a smooth fiber surface.
On the right, PI dissolves in NMP:DMAC 80:20 solvent system produces
small pits on the fiber surface. This surface roughness is due to differ-
ences between boiling points and electrical conductivity of NMP and
DMAC solvents (see Table 2). During the electrospinning process, these
solvents evaporate at different rates, and as a result, the fiber surface
solidifies at different rates generating a rough surface.
Several authors suggest that increasing the surface roughness of
electrospun PI nanofibers, it could be possible to increase their hydro-
phobicity [26,44,45]. We found that static water contact angle in-
creases as the roughness on the surface appear, as it can be seen in
bottom FE-SEM images in Fig. 6.
4. Conclusions
In this work, a complete study of the electrospinning process
parameters for aromatic PI using DoE and Teas solubility map was
carried out. Through both methodologies, it was determined the in-
dividual and mixed effects of four of the main electrospinning process
parameters on the morphology of the fibers, in order to assess the
electrospinning conditions that allows to produce defect-free PI nano-
fibers during a continuous process. This study was replicated with
different polymer solutions obtained with the best four solvents for this
PI (NMP, DMAC, DMF and DMSO). Regression analysis results em-
phasized that the polymer content and the applied voltage are the most
significant factors that affect the fiber diameter and the morphological
evolution of the electrospun mats (homogeneity).
Polymer concentration above 15 wt% provided more uniform fiber
morphology and reproducibility for all solvents systems evaluated.
However, it was observed that all solutions had different morphological
evolution according to the physicochemical properties of the solvents.
This is a result of their electrical conductivities, the inherent viscosity of
the solvent and the difference between the solubility parameters of the
polymer and the solvent. The entanglement concentration in the elec-
trospinning process was seen to differ significantly from one solvent to
J. Lasprilla-Botero et al. Materials Today Communications 14 (2018) 1–9

Fig. 5. FE-SEM micrographics of electrospun PI fibers obtained from 15 wt% PI solutions in binary solvent systems.

another. It was demonstrated that not all solvents with high solubility electrospinnability of its solutions are correlated in a Teas graph. This
for this PI produced good solutions to get defect-free fibers. solubility-electrospinnability map allowed for a systematic selection of
To the best of our knowledge [24,25,29–32], this is the first time solvents for developing binary solvent systems. By using this map
that the solubility behavior of a soluble PI commercial grade and the aromatic PI solutions with mixtures of solvents were designed to

7
J. Lasprilla-Botero et al.
electrospun defects-free PI nanofibers. These solutions produced fibers
with diverse fiber surface morphologies. Electrospun mats (membranes)
showing a rough surface morphology exhibited higher water contact
angle values than those with a smooth surface. From these results, we
concluded that by using solvent mixtures it is possible to control the
surface properties of electrospun mats, for customizing fibers for spe-
cific applications, such as hydrophobic membranes (surfaces) for oil-
water separation.
Acknowledgements
This study was supported by EAFIT University. The authors would
also like to thank to Colciencias through the National PhD scholarship
program and the MINECO project AGL2015-62855-C2-1-R for the fi-
nancial support of this work.
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