Materials 2015, 8, 4096-4117; doi:10.

3390/ma8074096
OPEN ACCESS

materials
ISSN 1996-1944
www.mdpi.com/journal/materials
Article

Synthesis and Process Optimization of Electrospun

PEEK-Sulfonated Nanofibers by Response Surface Methodology
Carlo Boaretti, Martina Roso, Alessandra Lorenzetti and Michele Modesti *

Department of Industrial Engineering, University of Padova, via Marzolo 9, 35131 Padova, Italy;
E-Mails: carlo.boaretti@dii.unipd.it (C.B.); martina.roso@unipd.it (M.R.);
alessandra.lorenzetti@unipd.it (A.L.)

* Author to whom correspondence should be addressed; E-Mail: michele.modesti@unipd.it;

Tel.: +39-049-827-5541; Fax: +39-049-827-5555.

Academic Editor: Maryam Tabrizian

Received: 22 May 2015 / Accepted: 30 June 2015 / Published: 7 July 2015

Abstract: In this study electrospun nanofibers of partially sulfonated polyether ether ketone
have been produced as a preliminary step for a possible development of composite proton
exchange membranes for fuel cells. Response surface methodology has been employed for
the modelling and optimization of the electrospinning process, using a Box-Behnken design.
The investigation, based on a second order polynomial model, has been focused on the
analysis of the effect of both process (voltage, tip-to-collector distance, flow rate) and
material (sulfonation degree) variables on the mean fiber diameter. The final model has been
verified by a series of statistical tests on the residuals and validated by a comparison
procedure of samples at different sulfonation degrees, realized according to optimized
conditions, for the production of homogeneous thin nanofibers.

Keywords: electrospinning; response surface methodology; sulfonated polyether ether ketone

1. Introduction

Nanofibers are an interesting and versatile class of one-dimensional nanomaterials, with diameters
ranging from tenths to hundreds of nanometers, which have been recognized as promising due to their
outstanding properties in terms of high porosity, excellent pore interconnectivity, small diameters and
high surface-to-volume ratio. Among the different nanofiber manufacturing technologies, electrostatic
Materials 2015, 8 4097

spinning, or electrospinning, represents the easiest, most promising [1] and versatile method for the
generation of aligned or randomly distributed nanofibers of a rich variety of different materials, such as
synthetic and natural polymers [2], composites [3], ceramics [4] and metals [5].
Electrospinning allows the production of nanofibers by applying a high electric field capable to
overcome the surface tension of a polymeric solution. When the voltage reaches a threshold value the
solution is deformed and produces an electrically charged jet that travels towards a grounded collector.
During this phase the jet undergoes a whipping process in which it is stretched and, thanks to the
evaporation of the solvent, produces a solid fiber. The morphology and diameter of the nanofibers
obtained by this technique depend on a wide range of parameters whose effect can be dependent on the
particular type of polymer/solvent system or can be influenced by the presence of interaction between
two or more parameters. The intrinsicly-complex nature of the process does not always lead to
satisfactory results from the applications of theoretical models, which can have limited descriptive
capability, and prevent a full understanding of the results from a one factor analysis.
Response surface methodology (RSM) is a collection of statistical and mathematical techniques
capable to allow the construction of an approximating model for the description of the relationship
between a response and a set of predictor variables, on the basis of empirical data obtained by an
appropriate experimental design. With RSM it is possible to carry out a simultaneous investigation of
the effect of the single variables and their mutual interaction, with the possibility to define quantitatively
optimized conditions to apply to a given process. In recent years, the application of this methodology
for the optimization of the electrospinning process has encountered a growing interest [6–13], due to its
easy implementation and the possibility to be adaptable to different polymer/solvent systems. Sulfonated
polyether ether ketone (sPEEK) is a sulfonated derivate of the polyaryl ether ketone family, which has
been recognized as a promising candidate for the replacement of Nafion for proton exchange membranes
(PEMs) due to its good conductivity and thermal stability. In this context the employment of
mechanically strong porous fiber matrix in composite PEMs represents one of the emerging and
promising strategies to provide mechanical strength and promote dimensional stability [14]. A mat of
homogeneous electrospun sPEEK nanofibers can provide a suitable reinforcing conductive matrix,
whose properties can be tailored according to its sulfonation degree. Additionally, a very thin fibrous
morphology is desirable because it can improve proton conductivity [15] or, in general, the electro-transport
of ions through the alignment of the ionic groups along the fiber axis domain, probably due to the high
shear forces responsible for the formation of thinner fibers. However, despite this potential interest
towards the application of such fibers, up to date only few literature works have reported the
electrospinning of sPEEK. Wang et al. [16] synthesized a sulfonated polyether ether ketone to produce
core-shell nanofibers for gas sensing. Stated the poor inherently electrospinnability of the polymer,
they coupled it with polyacrylonitrile in a weight ratio equal to 1:10 to produce nanofibers. Lee et al. [17]
electrospun a composite nanofiber mat of SiO2/sPEEK for fuel cell applications, starting from a solution
of sPEEK and SiO2 gel. They used very low flowrate (0.08 mL/h) and low relative humidity (below
15%) in order to obtain nanofibers. Chakrabarty et al. [18] have fabricated electrospun sPEEK
nanofibers for electro-dialytic separation of Na+ from Mg2+ or Ca2+ for potable water production.
Choi et al. [19] realized a highly performant composite PEM made of sPEEK and carbon nanotube webs
with a layer-by-layer deposition of such webs on electrospun sPEEK nanofibers subsequently fused by
Materials 2015, 8 4098

solvent exposure, while Li et al. [20] incorporated nanosilver particles in nanofibers and nanospheres of
a synthesized sPEEK for potential catalytic applications.
Apart from these few references no published work has been realized in order to explore and identify
the best conditions for the electrospinning of sPEEK. The purpose of the present study is to provide a
deeper insight regarding the electrospinning of sPEEK with a screening activity oriented to define the
range of parameters employable to obtain homogeneous thin nanofibers. The results obtained from this
study could thus be helpful as a preliminary step for the design of composite membranes for fuel cell or
electrodialysis applications.

2. Experimental Section

2.1. Materials

Polyether ether ketone (PEEK) (Mw = 20,800 g/mol, density = 1.32 g/cm3), sulfuric acid (95–97 wt %
conc.), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO)
and 1-Methyl-2-pyrrolidinone (NMP) were purchased from Sigma-Aldrich (St. Louis, MO, USA).

2.2. Preparation of Sulfonated PEEK

PEEK beads were pulverized with an analytical mill and dried at 100 °C overnight to remove possible
residual moisture. The sulfonation of PEEK (Figure 1) has been conducted according to the procedure
developed by Huang et al. [21].

O
H2SO4

O
n

O
SO 3H
O O O

O O
m 1m
O

Figure 1. Sulfonation of PEEK.

Tests were carried at three different temperatures (45 °C, 55 °C and 65 °C), taking a sample from the
reaction mixture every hour, up to a total of 5 h for each test. For every sample the polymer was recovered
by precipitating the solutions in a five-fold volume of ice-cold deionized water. The suspensions were
left in this state overnight and subsequently washed and filtered several times with deionized water until
the pH of the rinsed water was as close as possible to neutral. After the removal of the acid residues the
samples were dried in vacuum oven at 80 °C overnight and subsequently stored in a desiccator.
The evaluation of the sulfonation degree (DS) of the samples was carried by titration. About 0.2 g of the
samples were soaked in 100 mL of 0.1 M solution of NaCl, stirring the suspensions for 72 h to allow the
Materials 2015, 8 4099

complete conversion of the material in its sodium salt form. Titration was carried out with a 0.01 N
solution of NaOH, using phenolphthalein as an indicator. The uncertainty of the titration has been
estimated at ±2% by the error propagation method. The evaluation of the ion exchange capacity (IEC)
was carried according to the following equation:

(1)

where VNaOH is the volume of NaOH solution consumed (mL), CNaOH is the concentration of the NaOH
solution (mol/L), and Wsample is the dry weight of the sample (g). The sulfonation degree, which quantifies
the extent of the functionalization of the polymer, is defined as:

(2)

while the moles of sPEEK and PEEK in 1 g of sulfonated polymer can be expressed as [22]:

1000 (3)

1 0.001 369
(4)
288
where 369 and 288 are the molecular weights of the repetitive unit of sPEEK and PEEK in Daltons,
respectively.

2.3. Solubility Evaluation

The evaluation of the sPEEK solubility was carried in different polar aprotic solvents commonly used
for the dissolution of the polymer (DMF, DMAc, DMSO, NMP), according to the procedure of
Gong et al. [23]. The judgment of the solubility was carried out by taking into consideration different
sulfonation degrees and evaluating the results by a macroscopic inspection of the solutions.

2.4. Electrospinning Set-Up and Nanofibers Analysis

The electrospinning experiments have been carried out with a conventional apparatus, composed of
a syringe pump, a variable DC power supply, and a metal rotating collector in order to obtain a uniform
distribution of the fibers. A common 6 mL plastic syringe (Terumo) was mounted on the syringe pump
(Harvard 11 Pico Plus Syringe Pumps) and fitted with a 27G (Terumo, 0.4128 mm o.d, 0.21 mm i.d.)
stainless steel hypodermic needle. A variable DC power supply (Gamma High Voltage, Ormond Beach,
FL, USA) was used to produce a potential difference in the range of 0–30 kV. The positive (anode)
terminal was connected to the stainless steel needle using a steel spring-loaded clip with serrated jaws
(alligator clip), while the ground (negative) terminal of the power supply (cathode) was attached to the
rotating metal collector. The electrospinning apparatus was enclosed in a PMMA sealed chamber to
electrically insulate the system, to avoid air currents and maintain a stable environment. All the tests
have been conducted in a monitored environment, where both temperature and humidity were measured
constantly. The polymeric solutions were prepared by dissolving the samples overnight at room
Materials 2015, 8 4100

temperature in the selected solvents under intense stirring. The morphology of the electrospun samples
was characterized by scanning electron microscopy (SEM) (JSM 6490, Jeol Ltd., Tokyo, Japan)
micrographs of gold-sputtered samples deposited on aluminum foil. Fibers were measured by image
analysis with ImageJ software (version 1.48), taking a total of 200 diameters for each sample from
different photos.

2.5. Variables and Design Selection

The best conditions for the electrospinning of sPEEK were identified by conducting a preliminary
screening activity with a one-factor-at-a-time approach, considering both solution and process variables.
During this first phase, the aim was to identify a proper choice for the solvent and polymer concentration
and define a suitable range for the other variables considered, in order to have a stable electrospinning
process and a uniform fiber morphology. Once that those conditions were identified, the second part of
the study has been characterized by an experimental campaign based on a Box-Behnken Design
(BBD) [24,25]. In this case, to approximate the relationship between the response and the different
variables selected, a second-order linear model has been built according to the following general
equation [26]:

β β β β ε (5)

where y is the response of the design, xi and xj are the components of the vectors corresponding to the
different coded levels of the variables selected, k is the number of variables, βi and βii are the coefficients
associated to the linear and quadratic levels of the single variables while βij is the coefficient associated
to the interaction between pairs of variables. The term εij represents the statistical error associated to the
model, assumed to be an independent and identically-distributed random variable. The previous
expression makes use of coded levels of the variables which can be obtained by a simple transformation,
using the minimum and maximum values of the natural variables (zi) selected [27]:
max min /2
(6)
max min /2
This coding procedure is widely used for the fitting of linear regression models because all the
variables become dimensionless and their values fall between −1 and +1, allowing a better comparison
between the relevance of variables that, in their natural state, have different orders of magnitude and
units of measure. The present study is based on 4-variables-3-level BBD for the evaluation of the effect
of the following four variables: voltage, flow-rate, tip-to-collector distance, and sulfonation degree. The
choice of these variables has been done in order to evaluate the effect of the process parameters, which
could be specific for a given polymer/solvent system, and the effect of the sulfonation degree on the
final morphology and dimension of the nanofibers. The influence of the solution concentration has not
been screened in depth because it can be predominant over other factors and its effect on the final
morphology of the fibers is generally accepted and widely reported in the scientific literature [28–30].
In this regard the choice has been to select a concentration value capable to produce good and uniform
nanofibers and keep it constant at that specific value. For this number of factors and levels taken into
Materials 2015, 8 4101

consideration the choice of a BBD is more convenient, since it possesses features very similar to a classic
Central Composite Design but requires a lower number of runs, avoiding the employment of axial runs
and with the possibility of using only three evenly-spaced levels of the variables. The statistical analysis
of the experimental data has been conducted by employing Design Expert software (trial version 9.0.2,
Stat-Ease), using the mean fiber diameter and their standard deviation as response variables. The
statistical tests for the diagnostic of the developed model have been carried with R (The R Foundation
for Statistical Computing, version 3.1.2).

3. Results and Discussion

3.1. PEEK Sulfonation

According to the scientific literature [31,32], the most commonly used equation to express the
aromatic sulfonation rate in aqueous sulfuric acid is the following:
d
(7)
d
where [Ar] = concentration of the aromatic ring to be sulfonated, [H2SO4] = concentration of sulfuric acid,
Aw = activity of water (proportional to the concentration of water in the system), k = reaction rate constant
and t = reaction time. Sulfonation gives a better yield at elevated temperatures, especially in the case of
sulfonation to higher levels. In addition, the concentration of the sulfuric acid or oleum used as the
sulfonating agent influences the course of the reaction. Sulfonation prefers high concentrations of
sulfonating agents, while water, formed as a byproduct, reduces the rate of the reaction [21,33]. The
sulfonation of PEEK is an electrophilic aromatic substitution reaction in which the sulfonic acid groups
take place preferentially in one of the four position of the aromatic ring between the ether linkages of
the polymer repetitive unit, while the other two aromatic rings have low electron density due to the
electronic withdrawing effect of the adjacent carbonyl group [21]. The results of the experimental tests
at different temperatures are reported in Figure 2. As expected the kinetics improves by increasing the
temperature and generally shows a logarithmic relationship with time. The kinetics of the reaction has
been described with the model proposed by Shibuya and Porter [34,35], assuming a negative effect of
the sulfonated aromatic ring on the rate expression:
d
(8)
d
where c = concentration of the substrate (aromatic ring to be sulfonated) at time t, c0 = initial substrate
concentration, k1 = rate constant of sulfonation, kd = rate constant for the negative effect of the sulfonated
ring. By integration the equation becomes linear over time:
ln 1 (9)
where X represents the reaction conversion (or sulfonation degree) and K is the ratio between k1 and kd.
By converting the experimental data according to this formula it was possible to observe that they fall
along a line (Figure 3a), proving the coherence of the postulated model.
Materials 2015, 8 4102

Figure 2. Degree of sulfonation of PEEK in concentrated H2SO4 as a function of time and

temperature (onset of the time scale is from the complete dissolution of the polymer in acid).

In this manner, from the slopes of the linear approximation, it has been possible to obtain the ratio
k1/kd (Table 1), which can be used to re-fit the experimental data. The final fitting (Figure 3b) seems
quite satisfactory for the relatively low number of experimental points taken into consideration and it
has been proved to be more reliable with respect to other kinetics expressions that don't account for the
deflator effect [21].

(a) (b)

Figure 3. Kinetic modeling of the sulfonation reaction: (a) linearization of the kinetic
expression as a function of time, (b) comparison between the experimental data and the
model prediction (R2 = 0.98 for the data at 45 °C, R2 = 0.97 for the data at 55 °C, R2 = 0.99
for the data at 65 °C).

Table 1. k1/kd ratio obtained at different temperatures.

Temperature (°C) C0 (mol/L) k1/kd (mol/L·h)
45 0.183 0.0146
55 0.183 0.0308
65 0.183 0.0507

The values of the kinetic parameters obtained from this analysis are thus useful to predict the time
required to attain a given sulfonation degree of the polymer, according to one of the selected temperatures.
Materials 2015, 8 4103

3.2. sPEEK Solubility

PEEK is generally highly resistant to dissolution in most common solvents and for this reason its
solubility is generally limited to harsh solvents, especially strong acids like H2SO4, CH3SO3H and
HSO3Cl, which also act as reagents for its sulfonation [26]. Upon sulfonation the polymer becomes
progressively more polar with the increase of the sulfonation degree and can also be dissolved in polar
aprotic solvent with high dielectric constants. The solubility is not only a function of the sulfonation
degree but also of the concentration in the solution, which is mainly related to the molecular weight of
the polymer. A good solubility is necessary for electrospinning in order to have a stable solution during
the entire process for the production of the nanofibers. As can be seen from Table 2, to allow a complete
solubility in the solvents employed, a sulfonation degree of at least 55% is necessary. However, different
behaviors can be identified. For example DMSO and NMP seem to be able to interact more significantly
with the polymer at low sulfonation degrees, probably due to their high polarity. On the basis of the data
obtained from the reactions, three samples with a sulfonation degrees of about 60%, 70% and 80% were
taken into consideration for the subsequent analysis. These sulfonation degrees correspond, respectively,
to the samples sulfonated for two and three hours, at 55 °C, and for three hours, at 65 °C.

Table 2. Solubility of different sPEEK samples in different organic solvents (Sw. = swelling,
+ = partial solubility, ++ = complete solubility).
Sulfonation Degree DMF DMAc DMSO NMP
33% Sw. Sw. Sw. Sw.
45% Sw. Sw. + +
50% + + + ++
≥ 55% ++ ++ ++ ++

3.3. Electrospinning Screening

A first assessment to define the proper conditions for the electrospinning of the sulfonated polymer
has been carried out in order to identify the best solution concentration/solvent coupling to produce
homogeneous nanofibers. Due to the low molecular weight of the polymer high concentrations are
required in order to have a sufficient viscosity to allow the stretching of the solution and the formation
of a stable Taylor cone. For this reason the concentration range investigated was between 20 and
30 wt % and the results are shown in Table 3. As can be seen the morphologies of the samples are
influenced by the solvent chosen for a given concentration of the polymer solution.
Generally speaking, a concentration of at least 25% by weight of polymer in the solution is required
for the formation of fibers, with the only exception for the solutions with NMP, for which the minimum
concentration is 27% by weight. Below these values the fibers are highly heterogeneous, with the
presence of beads or a significant beads-on-fibers morphology. On the other hand even a concentration
of about 30% by weight is not recommended since the morphology changes, leading to the formation of
ribbons. This is true except for the case of NMP solutions, for which it appears clear that the
concentration interval for stable nanofibers is slightly higher than for the solutions of the other solvents.
A possible explanation for this is related to the properties of the solvent. NMP possesses a high surface
tension coupled to a high boiling point, compared to the other solvents chosen. This probably leads to a
Materials 2015, 8 4104

slower rate of solvent evaporation and the necessity to have a higher polymer concentration to increase
the viscosity of the solution. Indeed at a concentration of 25 wt % the fibrous morphology is present but
with a high concentration of defects. A comparison was also made by employing binary mixtures of the
selected solvents in a 50:50 weight ratio. In this case a concentration of about 27 wt % was chosen, since
it could be considered the value at which most of the solvents could produce a homogeneous fiber morphology.

Table 3. Morphology of the electrospun samples obtained during the screening phase
(sulfonation degree ≈ 70%, electrospinning condition: voltage = 20 kV, distance: 14 cm,
flow-rate: 0.125 mL/h).
Solution Solvent
Concentration DMF DMAc DMSO NMP
20 wt %
25 wt %
27 wt %
30 wt %

The results showed that the best morphology can be obtained by mixing DMF with DMAc (Figure 4a).
Only in this case the properties of the solvents and the polymer concentration can lead to the formation
of smooth and quite uniform fibers. The samples, electrospun with the DMF/NMP (Figure 4c) and
DMAc/NMP (Figure 4f) mixtures, present a beads-on-fiber morphology that gives fibers high
non-uniformity. Despite the fact that at a 27 wt % concentration the solution with only DMSO as solvent
produced ribbons instead of fibers, some samples of the mixture with DMSO were realized. Mixing
DMSO with DMAc (Figure 4d) at the given concentration, it is possible to produce fibers, even though
they seem irregular with significant variation of the diameter along a single fiber. The DMSO/NMP
(Figure 4e) samples presented the worst morphology due to the presence of both beads along fibers and
branched jets, in which smaller jets were formed on the surface of primary jets.
Materials 2015, 8 4105

(a) (b) (c)

(d) (e) (f)

Figure 4. SEM micrographs of polymer solutions with binary mixture (50:50 w/w) of
solvents (sulfonation degree DS ≈ 70%, electrospinning condition: voltage = 20 kV,
distance: 14 cm, flow-rate: 0.125 mL/h): (a) DMF/DMAc; (b) DMF/DMSO; (c) DMF/NMP;
(d) DMSO/DMAc; (e) DMSO/NMP; (f) NMP/DMAc.

From this first screening activity it has been possible to draw some preliminary conclusions regarding
the operative conditions to employ in order to obtain a stable and uniform fiber morphology of the
electrospun solutions. First, it is important to operate with low flow rates, usually with a maximum
values of 0.2 mL/h. This is necessary in order to obtain the production of a uniform deposition of fibers
since, with high flow rates, the process is not stable with a common range of voltages and it is likely to
result in the spraying of solution droplets from the tip of the syringe. In some cases, depending on the
type of solvent employed, even higher flow rates (0.4 mL/h) are employable, but this seems not to be a
good choice since, even if at the beginning the process is stable, once that a given amount of fibers are
produced and a small layer of mat is deposited, it probably acts as an insulating layer that decreases the
potential difference between the two electrodes, with a final effect that is comparable to a decrease in
the applied voltage. On the other hand it is also important to define a proper range of values for the
voltage. A good choice is to use voltages that are not lower than 15 kV, unless to employ a very low
tip-to-collector distance; otherwise, the spinning process is not stable over time. A maximum value of
30 kV has been chosen, which is usually the full-scale value for high-voltage supplies commonly
employed for electrospinning, and for safety reasons. The distances from the tip to the collector were
chosen by considering the necessity to provide a sufficient time of flight of the jet in order to stretch and
evaporate the solvent, for the lower level, and to be capable both of reaching the collector and to be
subjected to a sufficient electric strength in order not to generate drips, for the higher level. The
conditions that satisfied these requisites were defined in terms of 10 cm for the lower value and 18 cm
for the higher. Although not controlled to a specific level, it has been identified that relative humidity
Materials 2015, 8 4106

plays an important role for the electrospinning of the polymer. Best conditions are achieved at low levels
of humidity; otherwise, the deposition of the fibers is problematic and the nanofibers tend to form yarns
(Figure 5a), which subsequently aggregate to form a bundle (Figure 5b) from the tip electrospinning of
other sulfonated polymers [36] and ionomers [37,38]. The choice of the solvent to be employed is another
important aspect to define. The experimental tests have shown that DMF and DMAc, or a combination
of the two, could be good choices for the possibility of having a wider range of solution concentrations,
lower surface tensions and boiling points.

(a) (b)

Figure 5. Progressive formation of nanofiber yarns in conditions of high relative humidity:

(a) at the beginning and, (b) after several minutes of electrospinning.

The final conditions identified for a possible optimization of the sPEEK electrospinning have been
subsequently evaluated in depth with a statistical analysis based on the design of experiments (DoE)
approach in order to better identify which conditions can be employed to obtain high quality nanofibers.

3.4. The Box-Behnken Design

Once identified the conditions to allow a stable electrospinning process of the polymer, the following
step has been the determination of the variables’ influence on the fiber dimension by the employment of
a 4-variables-3-levels BBD. The solvent selected was DMAc, while the solution concentration was fixed
at the value of 26 wt %, since it has been identified as the lower value capable to produce fibers without
defects. Each run has been carried under controlled environmental conditions, with a relative humidity
below 30% and 21.3 ± 0.5 °C of temperature. The values of the other variables are reported in Table 4.
The experimental design consisted in 29 runs with 5 repetitions in the center point (Table 5).

Table 4. Variables chosen for the designed experiment.

Variable Symbol Lower Value Center Value Upper Value
Sulfonation degree (%) A 60 70 80
Voltage (kV) B 20 25 30
Distance (cm) C 10 14 18
Flow rate (mL/h) D 0.050 0.125 0.200
Coded value – −1 0 +1
Materials 2015, 8 4107

Table 5. Experimental matrix for the Box-Behnken design.

Run # A (%) B (kV) C (cm) D (mL/h) Mean (nm) Std. Dev. (nm)
1 60 20 14 0.125 181 32
2 80 25 10 0.125 166 35
3 70 25 14 0.125 164 29
4 70 20 14 0.200 167 35
5 80 25 14 0.200 205 50
6 80 25 14 0.050 192 32
7 60 25 10 0.125 218 50
8 70 30 14 0.050 182 36
9 70 25 14 0.125 167 25
10 70 25 14 0.125 171 28
11 70 20 18 0.125 179 38
12 70 20 14 0.050 189 34
13 60 25 14 0.200 193 27
14 70 30 18 0.125 190 45
15 70 25 14 0.125 167 25
16 70 25 10 0.200 184 40
17 60 25 18 0.125 199 33
18 60 60 14 0.125 187 32
19 70 25 18 0.050 225 40
20 70 25 14 0.050 201 55
21 80 25 18 0.125 222 54
22 70 25 18 0.200 216 60
23 70 30 10 0.125 172 38
24 70 25 14 0.125 170 29
25 70 30 14 0.200 182 35
26 80 20 14 0.125 170 33
27 80 30 14 0.125 171 31
28 70 30 10 0.125 173 37
29 60 25 14 0.050 233 46

The sequence of the runs were randomly defined by the software in order to highlight possible
external influences not taken into consideration in the design. The results of the image analysis have
shown that the variation of the variables selected produced mean fiber diameters ranging from about 165
to 235 nm and standard deviations ranging from 25 to 60 nm.

3.5. Analysis of the Mean Fiber Diameter

The first step in the evaluation of the response of the design has been carried by conducting an analysis
of variance (ANOVA) (Table 6), as a preliminary phase in the construction of a second-order model to
describe the response surface for the fitting of the experimental data. With this approach the statistical
significance of each variable selected and the possible interactions between them were evaluated with a
backward elimination method by retaining only those terms with a p-value ≤ 0.05 to reduce the
complexity of the polynomial expression.
Materials 2015, 8 4108

Table 6. ANOVA for response surface reduced quadratic model of the mean fibers diameter
(SS = sum of squares, Df = degrees of freedom, MS = Mean squares).
Source SS Df MS F-Value p-Value
Model 11782.88 11 1071.17 140.13 <0.0001
A-DS 720.75 1 720.75 94.29 <0.0001
B-Voltage 133.33 1 133.33 17.44 0.0006
C-Distance 1102.08 1 1102.08 144.17 <0.0001
D-Flow rate 481.33 1 481.33 62.97 <0.0001
AC 1369.00 1 1369.00 179.09 <0.0001
AD 784.00 1 784.00 102.56 <0.0001
BD 121.00 1 121.00 15.83 0.0001
A2 1891.17 1 1891.17 247.40 <0.0001
B2 502.31 1 502.31 65.71 <0.0001
C2 2003.55 1 2003.55 262.10 <0.0001
D2 3125.21 1 3125.21 408.84 <0.0001
Residual 129.95 17 7.64 – –
Lack of fit 96.75 13 7.44 0.90 0.6090
Pure error 33.20 4 8.30 – –

The estimation of the coefficients of the linear regression model was determined by a least square
minimization. The final refined model excluded the presence of the interaction terms AB and BC,
leading to the following final equation in terms of coded factors:
167.60 7.75 3.33 9.58

6.33 18.50 14.00

(10)
5.50 17.07 8.80

17.58 21.95
The adequacy of the regression model chosen for the description of the experimental results has been
confirmed by the value of 0.98 for the determination coefficient (R2) and the not significant lack of fit
(p-value = 0.6), with respect to the pure error. The obtained ratio of 40.062 for the adequate precision,
which measures the signal-to-noise ratio, is greater than 4 and indicates that the model can be used to
navigate in the design space. All the factors selected for the design have proven to be important in the
description of the variability in the data, although with different extents. Indeed, from the analysis of the
relative importance of the different regressors on the determination coefficient (Figure 6), voltage has
been identified as the factor that has less relevance with respect to the other terms of the model for both
its first-order, interaction and quadratic terms.
A similar result has been previously noted for the electrospinning of Bombyx mori silk [6] and PAN [8]
in relation to the employment of solutions with an high polymer concentration although the opposite
result has been found for the electrospinning of Poly(D,L-lactide) [7], probably due to a low tip-to-collector
distance [8]. Between the terms of different order the quadratic component is the most significant for the
prediction of the data, with a total contribution of about 60%. This result indicates the presence of strong
Materials 2015, 8 4109

curvature and optimal conditions probably not far from the center of the design space, in agreement with
the assumptions on which the BBD is based.

Figure 6. Proportionate contribution of each term of the quadratic model to the R2 statistic.

3.6. Diagnostic

After the definition of the refined model, a diagnostic phase has been carried out in order to evaluate
the assumptions at the basis of the procedure for the construction of the model by checking:
1. The normal distribution of the residuals
2. The absence of correlation of the residuals versus runs
3. The assumption of homoscedasticity (constant variance of the residuals)
The normal probability plot (Figure 7b) of the residuals seems to fit a straight line in quite a
satisfactory manner. A more reliable way to have a statistical indication of this assumption has been
found with the application of the Anderson-Darling test (ADT) [39].

(a) (b)

Figure 7. Cont.
Materials 2015, 8 4110

(c)

Figure 7. Diagnostic plots for the check of the consistency of the model developed:
(a) Residuals versus run for the check of the presence of time-related variable lurking in the
background, (b) Normal probability plot for the check of the normal distribution of the
residuals, (c) Residual versus predicted values plot for the check of the assumption of
constant variance of the residuals.

This test can be used to quantify the deviation of a set of residuals from a given distribution. In this
case it has been used to test the null hypothesis that the normal distribution adequately describes the
residuals, using the comparison of the calculated statistics with a critical value at a 5% level of
significance. For the present sample size of 29 residuals, the obtained p-value of 0.75 is higher than the
cut-off value of 0.05, confirming the conclusion drawn from the visual inspection of the normal
probability plot.
The assessment of the presence of autocorrelation in the residuals obtained from the linear regression
was realized with the Durbin-Watson test [40,41]. In this case, the statistic is used to evaluate the null
hypothesis that the residuals are not negatively nor positively correlated, at a 5% level of confidence.
According to the formula, the value of the statistic always falls between 0 and 4, and a value of 2 indicates
no presence of autocorrelation. In the present case the test gave a value of 1.99, which is very close to 2, and
indicates no significant autocorrelation [42]. A second control can be done, visually, from the plot of the
residuals versus the runs, which show no distinct increasing or decreasing pattern over time (Figure 7a). The
plot of the residuals versus the predicted values (Figure 7c), for the assumption of the constant variance,
doesn’t seem to present a specific increasing or decreasing funnel pattern so the final model has been
used without specific transformation of the data. In any case, a statistical evaluation of the
homoscedasticity condition has been carried with the Levene’s test [43] both for the residuals versus the
predicted values and for the comparison of the residuals’ variances at the different levels of each
regressor. In the first case, the violation of this condition should provide a different spreading of the
residuals along the predicted value axis and, to evaluate this, the interval has been divided into three
parts of equal extension, the residuals of each interval have been grouped, and their variances tested
against each other.
The resulting statistics give a value of 1.79 and a p-value of 0.4077 (higher than the threshold value
of 0.05), according to which it is not possible to reject the null hypothesis of equal variances. In the
second case, the test was applied by grouping the residuals according to the three different levels of the
Materials 2015, 8 4111

regressors and the corresponding variances tested between each other. The results of the test (Table 7)
reported a p-value higher than 0.05 for each of the regressors, excluding the possibility to reject the null
hypothesis of equal variances.

Table 7. Summary of the Levene’s test for the analysis of the homoscedasticity conditions
of the residuals of the different levels of the model regressors.
Regressor Levene’s Statistic p-Value
Sulfonation degree 4.907 0.086
Voltage 0.152 0.927
Distance 3.057 0.217
Flow-rate 0.603 0.740

3.7. Analysis of the Response Surface

From the polynomial model developed through the previous analysis it has been possible to construct
the response surface to analyze the effect of the different variables on the final mean diameter of the nanofibers.
The relationship between the DS and the tip-to-collector distance in Figure 8 shows that a decrease
of the mean diameter is accomplished by a combination of high sulfonation degrees and low distances,
independently from the different levels of the voltage employed because of the statistical insignificance
of the interaction terms AB and BC. For low sulfonation degrees, a possible improvement can be achieved
at medium distances but the final dimension of the fibers are generally greater than those at high
sulfonation degree for the same conditions of the other factors. However, this condition is verified for
low-medium values of the flow-rate because, for the highest level, the minimum of the response surface
shift towards the center of the design space, with a concurrent increment in the final mean fiber diameter.
A possible explanation can be related to the fact that an increase of the sulfonation degree of the
material is capable to provide an increase in the conductivity of the solution in a similar way to the
addition of a salt [20,44], leading to the formation of thinner fibers. Figure 9 presents the interaction
between the sulfonation degree and the flow-rate. In this second case, better and more stable conditions
are achieved by employing a low voltage coupled with low-medium distances, since the curvature of the
response surface is less significant and it is possible to obtain lower mean fiber diameters for a wider
range of flow rates and sulfonation degrees, with an higher flexibility of the process. This result can be
ascribed to the fact that, in this condition, an optimal balance between electric field strength, solvent
evaporation rate, and polymer jet stretching is achieved. For low flow rates the mean diameter increases
probably due to a non-equilibrium condition between the flow rate and the jet removal from the tip which
prevents the formation of a visible Taylor cone, with a more marked effect for low sulfonation degrees
where the solution conductivity is lower. For higher distances the response surface is flatter and the mean
diameter increases above the 200 nm. In the latter case, this effect is predominant on the different levels
of the other variables involved, determining non optimal conditions for the production of thin fibers.
Materials 2015, 8 4112

Figure 8. 3D response surface of the mean diameter for the sulfonation degree versus
distance at an applied voltage of 25 kV and a flow-rate of 0.125 mL/h.

Figure 9. 3D response surface of the mean diameter for the sulfonation degree versus
flow-rate at an applied voltage of 20 kV and at a distance of 14 cm.

The relationship between the voltage and the flow-rate, when the other variables at their medium
values, is reported in Figure 10, from which it is possible to observe a saddle shape of the response
surface. In this situation it is not possible to define unequivocally a specific optimal condition, but the
contour plot of the response surface seems to suggest that, for a given flow rate, lower mean diameters
could be obtained by operating with the lowest voltage value. The presence of a saddle shape of the
response is not uncommon during the analysis of the relationship between these two factors [10] and
several aspects need to be pointed out for the explanation of such behavior. An increment in the applied
voltage, when all the other variables are held constant, is traduced in an increment in the mass flow rate
ejected from the tip of the needle and a higher charge density. This induces an increment of the instability
and stretching of the jet which could produce smaller fiber diameters. However discrepancies between
the experimental results of several scientific works on the effect of the applied voltage for different
polymer/solvent systems could suggest the necessity to include a concurrent effect of other variables,
like feed rate and tip-to-collector distance, in the evaluation of such effect [45]. For the case in analysis
the interaction shows more significant variation when the flow rate is changed for a fixed voltage, rather
than the opposite case, stated the poor relevance of the voltage contribution term with respect to the flow
rate, on the developed model.
Materials 2015, 8 4113

Figure 10. 3D response surface of the mean diameter for the voltage versus flow rate at a
sulfonation degree of 70% and a distance of 14 cm from the tip to the needle.

3.8. Validation of the Model

Once analyzed, the behavior of the approximated response surface, in relation to the different levels
of the variables involved in the design, the final step has been the validation of the obtained model.
The objective of this validation has been to define constrained optimization conditions in order to obtain
uniform and thin sPEEK nanofibers for samples at a given sulfonation degree and comparing the results
from the values predicted by the software both in terms of mean diameter and standard deviation.
In order to define optimal conditions for the standard deviation of the analyzed samples, a response
surface was built based on a specific model developed for the data collected from the image analysis. In
this second case a quadratic model was found to be adequate to describe the data with and R2 value of 0.95.
The final equation excluded the presence of the voltage and showed the relevance of the interaction
terms between the sulfonation degree with distance and flow rate, as in the case of the model for the
mean diameter. The data have shown the presence of a positive correlation (correlation coefficient = 0.718)
between the mean diameter and the standard deviation, showing a good chance to obtain similar
conditions for the combined optimization. To this end, both the responses involved have been minimized
using a desirability function, defined as:
/∑

(11)

where N is the number of responses, ri is the value of the importance attributed to the selected response
and di is the partial desirability function for specific responses. For the case in analysis, the relative
importance selected was a value of 3 on a maximum value of 5, in order to set the optimization of the
process by defining an equal importance for both the two responses. The numerical optimization has
been carried via a penalty function approach using the downhill simplex method (Nelder-Mead method [46])
for multidimensional minimization. Three samples with different sulfonation degrees were selected and
the relative optimized conditions were set for the electrospinning experiments (Table 8).
Materials 2015, 8 4114

Table 8. Predicted optimized conditions and relative desirability function values for three
samples at different sulfonation degrees.
Sulfonation Degree Voltage Distance Flow-Rate
Sample Desirability
(%) (kV) (cm) (mL/h)
1 62 20 14.5 0.160 0.954
2 65 21 14.5 0.143 0.971
3 73 21 13.5 0.114 0.962

The results (Figure 11) have shown an acceptable accordance with the model prediction for the mean
diameter and, to a less extent, for the standard deviation, probably due to the low value (0.88) of the
predicted R2 of the relative model.

(a) (b)

Figure 11. Comparison between the experimental results and the model prediction
(prediction and 95% prediction interval) for: (a) the mean diameters and (b) the standard
deviation of electrospun nanofibers.

4. Conclusions

Sulfonation of polyether ether ketone with concentrated sulfuric acid has been accomplished as a
preliminary phase for the production of electrospun nanofibers for potential applications in the energy
field. The reaction has been modeled with a suggested kinetic expression that takes into consideration a
deflator effect of the sulfonated portion of the polymer, with a good fitting of the experimental data. The
modified polymer can be completely solubilized in different organic aprotic solvents for medium degrees
of sulfonation. The same solvents can be employed for the electrospinning of the material but with
different ranges of concentration, according to their specific physical properties. A first screening
activity has been carried out to select the proper set of variables for a subsequent, more careful, analysis
using a DoE approach. The general conditions for the electrospinning of the material require high
polymer concentrations, medium-high voltages, low flow-rates, and low relative humidity to allow a
proper collection of the nanofibers. A more detailed analysis has been carried out to develop a model for
the description of the response surface of the mean fiber diameter using a BBD in which both process
(voltage, tip-to-collector distance, flow-rate) and material (sulfonation degree) factors have been taken
into consideration. The developed model has shown a good descriptive capability of the observed data,
the presence of interaction between sulfonation degree, and both the flow rate and the distance
Materials 2015, 8 4115

parameters, while voltage has proven to have little or no effect on the final fibers dimensions. The model
showed a good capability in the description of the selected response changes in the design space and it
has been validated, in combination with a second model employed for the description of the standard
deviation, using optimized conditions for samples at different sulfonation degrees. Good results have
been obtained for the description of the first response while the standard deviation showed less
accordance to the predicted values. In this manner, it has been possible to define optimized conditions
in order to minimize the final mean diameter and standard deviation of the fibers according to the
different values of the sulfonation degree in the range analyzed.

Author Contributions

Carlo Boaretti and Martina Roso conceived and designed the experiments. Carlo Boaretti performed
the experiments. Carlo Boaretti, Martina Roso, Alessandra Lorenzetti and Michele Modesti analyzed
and discussed the data. Carlo Boaretti wrote the manuscript with revisions by Michele Modesti,
Martina Roso and Alessandra Lorenzetti.

Conflicts of Interest

The authors declare no conflict of interest.

References

1. Li, D.; Xia, Y. Electrospinning of nanofibers: reinventing the wheel? Adv. Mater. 2004, 16, 1151–1170.
2. Huang, Z.; Zhang, Y.; Kotaki, M.; Ramakrishna, S. A review on polymer nanofibers by electrospinning
and their applications in nanocomposites. Compos. Sci. Technol. 2003, 63, 2223–2253.
3. Chronakis, I. Novel nanocomposites and nanoceramics based on polymer nanofibers using
electrospinning process—A review. J. Mater. Process. Tech. 2005, 167, 283–293.
4. Dai, Y.; Liu, W.; Formo, E.; Sun, Y.; Xia, Y. Ceramic nanofibers fabricated by electrospinning and
their applications in catalysis, environmental science, and energy technology. Polym. Advan. Technol.
2011, 22, 326–338.
5. Wu, H.; Zhang, R.; Liu, X.; Lin, D.; Pan, W. Electrospinning of Fe, Co, and Ni nanofibers:
synthesis, assembly, and magnetic properties. Chem. Mater. 2007, 19, 3506–3511.
6. Sukigara, S.; Gandhi, M.; Ayutsede, J.; Micklus, M.; Ko, F. Regeneration of Bombyx mori silk by
electrospinning. Part 2. Process optimization and empirical modeling using response surface
methodology. Polymer 2004, 45, 3701–3708.
7. Gu, S.; Ren, J. Process Optimization and Empirical Modeling for Electrospun Poly(D,L-lactide)
Fibers using Response Surface Methodology. J. Macromol. Mater. Eng. 2005, 290, 1097–1105.
8. Yördem, O.; Papila, M.; Menceloğlu, Y. Effects of electrospinning parameters on polyacrylonitrile
nanofiber diameter: An investigation by response surface methodology. Mater. Design 2008, 29, 34–44.
9. Ray, S.; Lalman, J. Using the Box–Benkhen design (BBD) to minimize the diameter of electrospun
titanium dioxide nanofibers. Chem. Eng. J. 2011, 169, 116–125.
10. Roso, M.; Lorenzetti, A.; Besco, S.; Monti, M.; Berti G.; Modesti, M. Application of empirical
modelling in multi-layers membrane manufacturing. Comput. Chem. Eng. 2011, 35, 2248–2256.
Materials 2015, 8 4116

11. Nasouri, K.; Bahrambeygi, H.; Rabbi, A.; Shoushtari, A.M.; Kaou, A. Modeling and optimization
of electrospun PAN nanofiber diameter using response surface methodology and artificial neural
networks. J. Appl. Polym. Sci. 2012, 126, 127–135.
12. Konwarh, R.; Misra, M.; Mohanty, A.K.; Karak, N. Diameter-tuning of electrospun cellulose
acetate fibers: A Box–Behnken design (BBD) study. Carbohyd. Polym. 2013, 92, 1100–1106.
13. Kong, L.; Ziegler, G. Quantitative relationship between electrospinning parameters and starch fiber
diameter. Carbohyd. Polym. 2013, 92, 1416–1422.
14. Wycisk, R.; Pintauro, P.N.; Park, J. New developments in proton conducting membranes for fuel
cells. Curr. Opin. Chem. Eng. 2014, 4, 71–78.
15. Dong, B.; Gwee, L.; Salas-de la Cruz, D.; Winey, K.I.; Elabd, Y.A. Super proton conductive
high-purity nafion nanofibers. Nano Lett. 2010, 10, 3785–3790.
16. Wang, W.; Li, Z.; Jiang, T.; Zhao, Z.; Li, Y.; Wang, Z.; Wang, C. sulfonated poly(ether ether
ketone)/polypyrrole core-shell nanofibers: A novel polymeric adsorbent/conducting polymer
nanostructures for ultra-sensitive gas sensors ACS Appl. Mater. Inter. 2012, 4, 6080–6084.
17. Lee, C.; Jo, S.; Choi, J.; Baek, K.; Truong, Y.; Kyratzis, I.; Shul, Y. SiO2/sulfonated poly ether ether
ketone (sPEEK) composite nanofiber mat supported proton exchange membranes for fuel cells.
J. Mater. Sci. 2013, 48, 3665–3671.
18. Chakrabarty, T.; Kumar, M.; Rajesh, K.; Shahi, V.; Natarajan, T. Nano-fibrous sulfonated poly(ether
ether ketone) membrane for selective electro transport of ions. Sep. Purif. Technol. 2010, 75, 174–182.
19. Choi, J.; Lee, C.; Hawkins, S.C.; Huynh, C.P.; Park, J.; Jeon, Y.; Truong, Y.B.; Kyratzis, I.L.;
Shul, Y.G.; Caruso, R.A. Direct spun aligned carbon nanotube web-reinforced proton exchange
membranes for fuel cells. RSC Adv. 2014, 4, 32787–32790.
20. Li, X.; Hao, X.; Na, H. Preparation of nanosilver particles into sulfonated poly(ether ether ketone)
(S-PEEK) nanostructures by electrospinning. Mater. Lett. 2007, 61, 421–426.
21. Huang, R.Y.M.; Shao, P.; Burns, C.M.; Feng, X. Sulfonation of poly(ether ether ketone)(PEEK):
kinetic study and characterization. J. Appl. Polym. Sci. 2001, 82, 2651–2660.
22. Jiang, R.; Kunz, H.; Fenton, J.M. Investigation of membrane property and fuel cell behavior with
sulfonated poly(ether ether ketone) electrolyte: temperature and relative humidity effects. J. Power
Sources 2005, 150, 120–128.
23. Gong, C.; Guan, R.; Shu, Y.; Chuang, F.; Tsen, W. Effect of sulfonic group on solubility parameters
and solubility behavior of poly(2,6-dimethyl-1,4-phenylene oxide). Polym. Adv. Technol. 2007, 18,
44–49.
24. Box, G.; Behnken, D. Some new three level designs for the study of quantitative variables.
Technometrics 1960, 2, 455–475.
25. Box, G.; Draper, N. Empirical Model-Building and Response Surfaces. In Wiley Series in
Probability and Statistics; Wiley: New York, NY, USA, 1987.
26. Bishop, M.; Langley, K. Solubility and properties of a poly(aryl ether ketone) in strong acids.
Macromolecules 1985, 18, 86–93.
27. Myers, R.; Montgomery, D.; Anderson-Cook, C. Wiley Series in Probability and Statistics; Wiley:
Hoboken, NJ, USA, 2009.
28. Fong, H.; Chun, I.; Reneker, D. Beaded nanofibers formed during electrospinning. Polymer 1999,
40, 4585–4592.
Materials 2015, 8 4117

29. Deitzel, J.; Kleinmeyer, J.; Harris, D.; Beck Tan, N.C. The effect of processing variables on the
morphology of electrospun nanofibers and textiles. Polymer 2001, 42, 261–272.
30. Lee, K.; Kim, H.; Bang, H.; Jung, Y.; Lee, S. The change of bead morphology formed on
electrospun polystyrene fibers. Polymer 2003, 44, 4029–4034.
31. Cerfontain, H. Mechanistic aspects in aromatic sulfonation and desulfonation. In Interscience
Monographs on Organic Chemistry Series; Interscience Publishers: New York, NY, USA, 1968.
32. Compton, R.; Bamford, C.; Tipper, C. Reaction of aromatic compounds. In Comprehensive
Chemical Kinetics: Volume 13; Elsevier: Amsterdam, The Netherland, 1972.
33. Kučera, F.; Jančar, J. Homogeneous and heterogeneous sulfonation of polymers: A review.
Polym. Eng. Sci. 1998, 38, 783–792.
34. Shibuya, N.; Porter, R. Kinetics of PEEK sulfonation in concentrated sulfuric acid. Macromolecules
1992, 25, 6495–6499.
35. Shibuya, N.; Porter, R. A reconsideration of the kinetics of aromatic sulfonation by sulfuric acid.
Macromolecules 1994, 27, 6267–6271.
36. Subramanian, C.; Weiss, R.; Shaw, M.T. Electrospinning and characterization of highly sulfonated
polystyrene fibers. Polymer 2010, 51, 1983–1989.
37. Okuzaki, H.; Takahashi, T.; Miyajima, N.; Suzuki, Y.; Kuwabara, T. Spontaneous formation of
Poly(p-phenylenevinylene) nanofiber yarns through electrospinning of a precursor. Macromolecules
2006, 39, 4276–4278.
38. Laforgue, A.; Robitaille, L.; Mokrini, A.; Ajji, A. Fabrication and characterization of ionic
conducting nanofibers. Mater. Eng. 2006, 292, 1229–1236.
39. Anderson, T.; Darling, D. Asymptotic theory of certain goodness-of-fit criteria based on stochastic
processes. Ann. Math. Statistics 1952, 23, 193–212.
40. Durbin, J.; Watson, G. Testing for serial correlation in least squares regression, I. Biometrika 1950,
37, 409–428.
41. Durbin, J.; Watson, G. Testing for serial correlation in least squares regression, II. Biometrika 1951,
38, 159–179.
42. Yetilmezsoy, K.; Demirel, S.; Vanderbei, R. Response surface modeling of Pb(II) removal from
aqueous solution by Pistacia vera L.: Box-Behnken experimental design. J. Hazard. Mater. 2009,
171, 551–562.
43. Levene, H. Robust tests for equality of variances. In Contributions to Probability and Statistics;
Stanford University Press: Stanford, CA, USA, 1960.
44. Li, X.; Hao, X.; Xu, D.; Zhang, G.; Zhong, S.; Na, H.; Wang, D. Fabrication of sulfonated poly(ether
ether ketone ketone) membranes with high proton conductivity. J. Membrane Sci. 2006, 281, 1–6.
45. Andrady, A. Science and Technology of Polymer Nanofibers; Wiley: Hoboken, NJ, USA, 2008.
46. Press, W.H.; Flannery, B.P.; Teukolsky, S.A.; Vetterling, W.T. Numerical Recipes in Pascal:
The Art of Scientific Computing; Cambridge University Press: New York, NY, USA, 1989.

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