Journal of ELECTRONIC MATERIALS, Vol. 48, No.

6, 2019
https://doi.org/10.1007/s11664-019-07124-7
 2019 The Minerals, Metals & Materials Society

Response Surface Methodology as a Powerful Tool

for the Synthesis of Polypyrrole-Doped Organic Sulfonic Acid
and the Optimization of its Thermoelectric Properties

ZAKARIA BEKKAR DJELLOUL SAYAH,1,2 AHMED MEKKI,1,3

FABIEN DELALEUX,2 OLIVIER RIOU,2 and JEAN-FELIX DURASTANTI2,4

1.—Ecole Militaire Polytechnique, BP 17 Bordj El-Bahri, 16046 Alger, Algeria. 2.—Centre

d’Etudes et de Recherche en Thermique Environnement et Systèmes (CERTES), IUT de Sénart,
Universite Paris-Est, rue Georges Charpak, 77567 Lieusaint, France. 3.—e-mail:
mekki_ahmedkarim@yahoo.fr. 4.—e-mail: durastanti@u-pec.fr

In the present study, we aimed to fix the trigger parameters in the chemical
synthesis of polypyrrole (PPy) using response surface methodology (RSM),
based on central composite design (CCD) for high thermoelectric properties at
room temperature up to 373 K. The RSM experimental design involved the
investigation of three selected parameters [reaction time (t), oxidant (O) and
dopant (D) concentrations] simultaneously. For this purpose, many reactions
were performed in order to obtain thermoelectric efficiency responses, the so-
called figure of merit (ZT). The bulk’s properties including electrical conduc-
tivity (r), thermal conductivity (j) and Seebeck coefficient (S) were respectively
determined using the four-probes method, hot disc technique, and a homemade
device. A second-order polynomial equation was used to model the relationship
between the synthesis parameters and the figure of merit (ZT). A satisfactory
R2 value of 0.83 was obtained from the regression analyses, suggesting good
correlation between observed experimental values and predicted values by the
second-order polynomial. The linear, quadratic and interaction terms of the
considered parameters have a significant effect (P < 0.05) on the figure of merit
(ZT). A reaction time of 20 min, an oxidant concentration of 0.1 mol and a dopant
concentration of 0.005 mol were found to be the combinatorial optimal param-
eters for PPy synthesis resulting in improved thermoelectric properties, where
the maximum value of the figure of merit (ZT) was around of 2.71 9 106.
Moreover, several techniques like Fourier transform infrared (FTIR) spec-
troscopy, Raman spectroscopy, x-ray photoelectron spectroscopy (XPS) and
scanning electron microscopy were performed to characterize optimized PPy,
and its characteristics were then correlated with their bulk properties.

Key words: Response surface methodology (RSM) polypyrrole/DBSA,

thermoelectric efficiency, figure of merit (ZT)

have reported increased infatuation by emerging

INTRODUCTION
Nowadays, reports on energy forecasts are alarm-
ing in regard to the lack of worldwide conventional
energy resources. Particularly, statistical studies
(Received November 16, 2018; accepted March 8, 2019;
published online March 20, 2019)
countries over recent years, causing the fast
decrease of energy reserves and the high cost for
exploration of new technologies.1 With a similar
situation, efforts must entail finding new practica-
ble alternatives in the very near future, at least to
be able to make a balance in the energy market.
Hence, all attentions are riveted to the energy
production process based on photovoltaics,2,3 fuel

3662
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties
cells,4 wind turbines,5 and biomass.6,7 In recent
years, thermoelectricity has appeared as a promis-
ing alternative.8,9 It offers a way to convert waste
heat energy into electrical power,10,11 based on the
Seebeck effect. Semiconductor compounds like
Si1x Gex alloys, half-Heusler compounds, skutteru-
dites and tellurides like Bi2 Ti3 and PbTe are
recognized to be the best materials,12 based on their
efficiency. Generally, the thermoelectric efficiency is
quantified by dimension-less thermoelectric figure of
merit,13,14 defined as:
S2 r
ZT ¼ T ð1Þ
j
where S, r, j, and T are respectively the Seebeck
coefficient, the electrical conductivity, the isother-
mal conductivity and the absolute temperature.
Since the 1990s, a large number of researches have
been conducted aiming at enhancing the thermo-
electric efficiency of inorganic material, through
improving the Seebeck coefficient and reducing
thermal conductivity by increasing the scattering
of phonons.15 These efforts have put forward the
significant role of geometry optimization and reduc-
tion of the physical dimensionality of the material.
Although significant improvement has been made,
the conversion efficiency of thermal energy to
electrical energy is still lower than the maximum
required by Carnot efficiency.16 Moreover, the pro-
gress of inorganic materials has not realized any
increase because of their expensive cost, scarcity
and/or toxicity, and the difficulty of their
processing.17
Lately, another important category of thermoelec-
tric materials mainly includes organic material-
based conducting polymers (CPs) and their compos-
ites; these compounds have experienced a rapid
ascension,18 making them potential candidates sub-
stituting for inorganic materials. This class of
materials present versatile advantages, such as
the raw materials’ availability, lack of toxicity,
solution treatment, good flexibility, low cost, light-
weight, adjustable molecular structure and low
thermal conductivity (j).19 In addition to these
characteristics, another factor known as power
factor (PF) estimated by the multiplication product
of (S2r) is used to replace the figure of merit (ZT) for
the thermoelectric performance assessment. Several
intrinsically conducting polymers (ICPs) demon-
strated a significant enhancement in their thermo-
electric properties, via their increase in the figure of
merit by orders of magnitude, reaching values close
to those of inorganic materials.20
To date, the main conducting polymers applied as
thermoelectric materials are, poly(3,4-ethylene-
dioxythiophene) (PEDOT), polyaniline (PANI),21
polypyrrole (PPy)22 and polythiophene (PTH).23,24
Amongst all of them, PPy affords promising char-
acteristics,25,26 which broadens its usage in other
3663
applications related to the anti-electrostatic coat-
ings,27 batteries,28 sensors29–31 …etc.
Moreover, the efficiency of PPy depends largely on
the competition of multiple factors.32 Indeed, many
works highlight the effect of the material doping
level33 on conductivity values. However, they have
omitted the important influence of reaction time,
and the interaction effect of both oxidant and
dopant concentrations, which have not been stated
elsewhere. Optimization of significant influencing
factors on the thermoelectric behavior of polymers is
of great interest. Some attempts emphasize the
contribution from the monomer concentration, and
the polymer morphologies.34 However, studying
such variable parameters requires considerable
quantity of raw material and is time-consuming.
Thus, researchers are making recourse to the
optimization technique,35 in order to overcome these
hindrances.36 Response surface methodology (RSM)
is widely used for experimental design and opti-
mization processes, via combining mathematical
modeling and statistical techniques.37–39 It is con-
sidered as the faster and less laborious technique,
requiring minimum experimental procedures for
optimization of multiple independent variables.
The shortcoming of detailed information regard-
ing the enhancement of thermoelectric perfor-
mances of conducting polymers, based on the
consideration of their synthesis parameters, has
motived the present study. We report in this study a
synthesis procedure based on RSM and reduced
number of experimental runs, aiming at evaluating
the relationship between the effect of different
pyrrole polymerization parameters taken alone
and the resulting thermoelectric figure of merit
(ZT), therewith considering also the interaction
effects among the independent parameters. There-
after, the chemical characteristics of optimized PPy
were correlated with its measured bulk properties
(electrical conductivity and Seebeck coefficient) by
several techniques such as Fourier transform infra-
red (FTIR) spectroscopy, Raman spectroscopy, x-ray
photoelectron spectroscopy (XPS) and scanning
electron microscopy (SEM). The entire, selected
synthesis parameters have proven to be effective
for reaching precisely the aimed thermoelectric
performances.
EXPERIMENT
Materials and Methods
Pyrrole (purchased from Sigma-Aldrich, purity >
98%) was subjected to distillation under reduced
pressure and then stored at 4C in the dark prior to
synthesis. Dodecylbenzene sulfonic acid (supplied
by Sigma-Aldrich, purity > 98%) and iron chloride
hexahydrate were used as received. Organic sol-
vents were of analytical grade. Deionized (DI) water
was used throughout the synthesis steps for solu-
tion preparation and washing.
3664
Characterization and Thermoelectric Perfor-
mances Determination
The electrical conductivity (r) was measured
using the conventional four-probes technique with
a Jandel RM 3000 (with typical probe separation of
1 mm).
Thermal conductivity (j) was determined using
the hot-disc 2500S method according to the stan-
dard test method. This method is valid for measur-
ing thermal conductivities of polymeric materials
with values within the range 0.1–1 W.m1.k1. The
Seebeck coefficient was determined using a home-
made apparatus (see Fig. 1), wherein the tempera-
ture was determined using embedded
thermocouples in a heating cartridge controlled by
supplied stabilized current, and a Keithley multi-
meter/switching system; the cooling system was
ensured by the circulation of cold water through a
copper coil and using an RS 360 water pump. In
order to obtain precise values, the apparatus was
subject of validation procedures conducted on cop-
per plates samples with known values. The Seebeck
coefficient is the slope of linear regression of elec-
trical potential DV, as a function of temperature,
DT  10 K, and is given by the following equation:
DV
S¼
DT
For thermoelectric measurements (electrical con-
ductivity and Seebeck coefficient), a hydraulic press
and homemade mold were used to prepare PPy
Fig. 1. Schematic presentation of homemade apparatus for Seebeck coefficient measurement.
Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti
pellets by cold-pressing the powder samples at
20 MPa.
Raman spectroscopy was carried out using a
Thermo-Fisher DXR 2 spectrometer; excitation
was at 532 nm from a He–Ne laser at room tem-
perature. Fourier transform infrared (FTIR) spectra
were collected in attenuated total reflection (ATR)
mode in the wave number range 4000–600 cm1
with a nominal resolution of 4 cm1 over 50 scans,
using a Perkin Elmer 100 spectrometer. Sample
morphology was observed using an FEI-Quanta 600
scanning electron microscope under an acceleration
voltage of 15 kV and at a working distance of 14 nm.
Elementary composition analysis was determined
using x-ray photoelectron spectroscopy (XPS,
Thermo Scientific ESCALAB 250Xi).
Polypyrrole Synthesis and Statistical Analysis
Design
As shown in Fig. 2, the chemical oxidative method
was used for the PPy synthesis. In typical synthesis
procedures, 100 mL of dodecylbenzene sulfonic acid
aqueous solution is mixed with a solution of iron
chloride hexahydrate dissolved in 100 ml of DI
water. Then, the obtained mixture was kept under
magnetic stirring for 15 min at a temperature of 0
C. Subsequently, we added dropwise a precooled
ð2Þ
solution of 0.1 mol of pyrrole monomer to the
previous solution, kept under stirring during differ-
ent reaction times, allowing the polymerization
reaction to proceed. Finally, filtration of resulting
black precipitate was performed, followed by rinsing
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties
Fig. 2. Illustrative scheme for polypyrrole synthesis procedure.
with DI water several times until the filtrate
solution was colorless. The resulting product was
dried under vacuum at 80C for 8 h. Upon collecting
each sample, FTIR and Raman spectroscopy anal-
yses were carried out in order to characterize the
obtained product structure.
In order to obtain optimized thermoelectric prop-
erties of PPy, the synthesis PPy conditions were
followed by employing central composite design
(CCD) techniques, which considers an independent
variables packet. The reaction time (T), oxidant
concentration (O) and dopant concentration (D) are
the input variables, and their levels and ranges
were set as follows: reaction time was varied from
20 to 60 min, oxidant concentration was taken at
three different values (0.05, 0.075 and 0.1) and
dopant concentration was equal to 0.005, 0.0075 and
0.01).
Aiming to produce a polymer with an optimal
conductivity and, consequently, an important ther-
moelectric effect, the choice of our experimental
design was based on results obtained in earlier
work. In fact, the synthesis of PPy has been studied
3665
from different sides, through which several
researchers have considered the oxidant, the dopant
and the polymerization time effect on the reaction
efficiency and the electrical conductivity of the
material. Studies were conducted for molar ratios
of oxidant/monomer ranging between 1:1 and
1:6,40,41 or molar ratios of dopant/monomer varied
between 1:10 and 1:25,42,43 and for a polymerization
time up to 24 h.27,40,44
The formulated experimental design was based on
CCD with a total number of treatment combinations:
N ¼ 2k þ 2k þ nc : ð3Þ
where k is the number of treatment factors (k = 3),
nc is the replicates number of treatment combina-
tions at the center (nc = 6), which are very neces-
sary for the estimation of ‘‘pure error.’’ And 2 is the
number of axial points in the axis of each treatment
factor, at a distance of a (a = 2(k/4) = 2(3/4) = 1.682)
from the design center.45 The coded and actual
factors used for this experiment are given in
Table I.
3666 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

Table I. Experimental ranges of the independent variables used in the central composite design (CCD) for
polypyrrole synthesis
Level

Factor Code (parameter) 21.682 (2a) 21 0 1 1.682 (a)

Reaction time (min) T 6.364 20 40 60 73.636

Oxidant concentration (mol) O 0.033 0.05 0.075 0.1 0.117
Dopant concentration (mol) D 0.0033 0.005 0.0075 0.01 0.0117

Table II. Central composite design matrix of factors and figure of merit ZT for the synthesized PPy
Time, Molar re- Molar re-
Standard Run X1 [O], X2 port (O:M*), [D], X3 port (D:M*), Coded pro- ZT Predicted
order order (min) (mole) X2 (mole) X3 cess factors (1026) ZT (1026)

1 3 20 0.05 1:2 0.005 1:20 1 1 1 0.92 0.55

2 15 60 0.05 1:2 0.005 1:20 1 1 1 0.25 0.14
3 8 20 0.1 1:1 0.005 1:20 1 1 1 2.71 2.21
4 1 60 0.1 1:1 0.005 1:20 1 1 1 1.21 0.84
5 9 20 0.05 1:2 0.01 1:10 1 1 1 1.47 1.21
6 19 60 0.05 1:2 0.01 1:10 1 1 1 1.28 1.14
7 5 20 0.1 1:1 0.01 1:10 1 1 1 2.76 2.29
8 16 60 0.1 1:1 0.01 1:10 111 1.46 1.26
9 10 6.364 0.075 1:1.5 0.0075 1:15 1.682 0 0 1.05 1.69
10 18 73.636 0.075 1:1.5 0.0075 1:15 1.682 0 0 0.32 0.48
11 20 40 0.033 1:2.33 0.0075 1:15 0 1.682 0 0.38 0.55
12 11 40 0.117 1:0.66 0.0075 1:15 0 1.682 0 1.37 2.00
13 17 40 0.075 1:1.5 0.0033 1:23.3 0 0 1.682 0.12 0.64
14 4 40 0.075 1:1.5 0.0117 1:6.6 0 0 1.682 1.31 1.59
15 12 40 0.075 1:1.5 0.0075 1:15 000 0.25 0.24
16 6 40 0.075 1:1.5 0.0075 1:15 000 0.26 0.24
17 2 40 0.075 1:1.5 0.0075 1:15 000 0.22 0.24
18 13 40 0.075 1:1.5 0.0075 1:15 000 0.29 0.24
19 7 40 0.075 1:1.5 0.0075 1:15 000 0.3 0.24
20 14 40 0.075 1:1.5 0.0075 1:15 000 0.25 0.24
(*) M: design monomer concentration.

Design Expert software was used to design the
total number of 20 experiments [N = 23 +
(2 9 3) + 6 = 20] and analyze the experimental
data.
The standard and run orders, variable factors,
determined figure of merit (ZT) and its predicted
values are shown on Table II.
The mathematical relationship between the inde-
pendent variables and the obtained responses in
terms of figure of merit (ZT), were established by
fitting the experimental data to a second-order
polynomial equation as given by:
X X XX
Y ¼ b0 þ b i Xi þ Bii Xi2 þ bij Xi Xj ð4Þ
where Y is the response variable, b0 is the constant,
and bi, bii and bij represent the linear, quadratic
and interactive coefficient, respectively. Xi and Xj
represent the independent variables.
Moreover, multiple regression analysis, analysis
of variance (ANOVA for response surface reduced
cubic model), and determination of coefficient R2 for
the estimation of the model fit regression were done
by using the same software, Design Expert. The
total error criteria with a confidence level of 95%
were the basis for statistical test significance.
Table II lists the run order, variables factors,
determined figure of merit (ZT) and its predicted
values.
RESULTS AND DISCUSSION
As shown in Fig. 3, FTIR spectra of PPy samples
(obtained by the combination of different reaction
times, varied molar concentrations of oxidant, and
varied molar concentrations of dopant) are almost
the same, suggesting the same molecular structure.
Note the clear appearance of the principal bands at
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped 3667
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties

1553 cm1 and 1468 cm1 attributed to the sym-
metric and antisymmetric elongation of the pyrrole
cycle.
Table III summarizes room temperature mea-
surements of electrical conductivity and thermo-
electric properties (thermal conductivity and
Seebeck coefficient) of samples.
Model Analysis
The multiple regression coefficients obtained by
the application of least squares technique in order to
Fig. 3. FTIR spectra of prepared PPy samples according to their
coded factors. (Unit normalization is done by changing the range of
intensity values, where the maximum values is in each spectrum is
equal to one).
predict model for the figure of merit (ZT) based on
second-order polynomial equation are listed in
Table IV. Values of (P < 0.05) indicate that both
effects rising from reaction time, oxidant molar
concentration and dopant molar concentration on
the figure of merit ZT are significant.
The regression coefficients R2 of 0.83 indicate that
the regressed model of figure of merit ZT is accept-
able and corresponds to the experimental results.
Furthermore, application of the regression model
found for the figure of merit permits the comparison
of its predicted results with the experimentally
determined of figure of merit, where they have been
found to be approximately the same, as presented in
Table V.
Figure of merit (ZT) evolution is tributary to
effects gained from linear, quadratic and interaction
of the studied variables. Hence, after considering
the determined coefficients, we write the second-
order polynomial given in Eq. 4 as follows:
 
ZT 106 ¼ 3:7550:054X1 32:623X2 511:147X3
0:485X12 þ 1:7X13  2560X23 þ 0:00075X12
þ 589:729X22 þ 49921:923X32
ð5Þ
where the negative signs indicate the antagonistic
effects, while the positive signs indicate the syner-
gistic effects.
When analyzing the presented results in Table
IV, we reveal a P value of 0.0075, which indicates
that the model is highly significant. There is only
0.75% chance that a ‘‘lack of fit F-value’’ occurs due
to noise.

Table III. Matrix of factors and related responses of ZT for synthesized PPy
N° Sample (coded factor) S (lV/K) r (S/cm) j (W/m K) PF (W/m K2).10210 ZT .1026

1 1 1 1 1.12 4.46 0.181 5.59 0.92

2 1 1 1 0.705 3.119 0.183 1.55 0.25
3 1 1 1 1.067 7.538 0.0943 8.58 2.71
4 1 1 1 1.23 3.65 0.136 5.52 1.21
5 1 1 1 2.45 1.864 0.226 11.19 1.47
6 1 1 1 0.854 5.54 0.094 4.04 1.28
7 1 1 1 1.19 6.667 0.102 9.44 2.76
8 111 0.825 7.519 0.104 5.12 1.46
9 1.682 0 0 2.03 1.869 0.219 7.70 1.05
10 1.682 0 0 0.716 3.43 0.162 1.76 0.32
11 0 1.682 0 0.816 3.31 0.172 2.20 0.38
12 0 1.682 0 0.811 7.722 0.11 5.08 1.37
13 0 0 1.682 0.728 1.148 0.149 0.61 0.12
14 0 0 1.682 0.873 5.618 0.097 4.28 1.31
15 000 0.894 2.087 0.199 1.67 0.25
16 000 1.111 2.381 0.34 2.94 0.26
17 000 0.84 2.01 0.192 1.42 0.22
18 000 1.11 2.632 0.33 3.24 0.29
19 000 0.782 3.36 0.201 2.05 0.3
20 000 0.714 3.222 0.195 1.64 0.25
3668 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

The values of P ranging from 0.01 to 0.05
(0.01 < P < 0.05) indicates that the reaction time,
the oxidant’s molar concentration and the dopant
concentration had significant effect the on figure of
merit ZT, and signify that X1, X2, X3, X21, X22 and X23
are significant model terms.
Regarding the interaction effects study, either
considering single parameters or a number of
assembled parameters, it is deduced from P values
(P > 0.05) that the interactions between the reac-
tion time and the oxidant’s molar concentration,
oxidant’s molar concentration and dopant molar
concentration, and reaction time within the exper-
imental range, were not significant.
The analysis of a three-dimensional response
surface graph and a two-dimensional contour
plotted from the linear, quadratic and the inter-
action terms of the determined second-order
polynomial model is used to select the maxi-
mum, minimum and saddle points of the
response, and evaluate the variables’ impact on
the response. It helps to observe interactions
between two factors by holding the third one
constant at its considered center level. However,
it is found out that only the two-dimensional
plot is more suitable for the determination of the
responsibility degree of each variable on the
desired response.

Table IV. Estimated regression coefficients, corresponding P values and analysis of variance for the final
regression model of ZT
Term Coefficients (coded factors) Coefficients (actual factors) Standard error P value *

b0 0.24 3.75483 0.19 0.0075

X1 ðb1 Þ 0.36 0.05455 0.12 0.0159
X2 ðb2 Þ 0.43 32.62264 0.12 0.0058
X3 ðb3 Þ 0.28 511.14722 0.12 0.0442
X12 ðb12 Þ 0.24 0.48500 0.16 0.1639
X13 ðb13 Þ 0.09 1.7 0.16 0.6099
X23 ðb23 Þ 0.16 2560 0.16 0.3449
X12 ðb11 Þ 0.30 0.00075 0.12 0.0311
X22 ðb22 Þ 0.37 589.7289 0.12 0.0119
X32 ðb33 Þ 0.31 49921.92325 0.12 0.0267
R2 0.83
Adj:R2 0.67
* P< 0.01 highly significant; 0.01< P< 0.05 significant; P > 0.05 not significant.

Fig. 4. (a) Response surface and (b) contour plot for the figure of merit (ZT) as a function of oxidant molar concentration and reaction time at a
fixed dopant concentration equal to 0.01 mol.
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties
Fig. 5. (a) Response surface and (b) counter plot for the figure of merit (ZT) as a function of dopant concentration and reaction time at a fixed
oxidant concentration equal to 0.075 mol.
Figure 4 depicts the counter plot and the response
surface of the oxidant’s molar concentration and the
reaction time effect on the figure of merit, at a fixed
dopant molar concentration equal to 0.01 mol. The
improved values of figure of merit (ZT) around
1.63 9 106 until 1.94 9 106 are observed at a
reaction time of 20 min and an oxidant concentra-
tion included between 0.09 and 0.1 mol. These
observations are possibly due to: (1) the pyrrole
polymerization rate is related to the concentration
of the oxidant, and it could be increased by the
addition of an excess of oxidant, according to
previous study.46 At such concentration, the pres-
ence of oxidant anions is essential for the way in
which the doping species will be incorporated into
the polymer instead of the oxidant anions, and
hence it will determine its good conductivity and
stability. (2) According to pyrrole polymerization
kinetics,47 it seems that within an equilibrium
reaction time around 20 min and the optimum
oxidant concentration, pyrrole polymerization
reached its high mass quantity. (3) The combination
of the two cited conditions affect the pyrrole poly-
merization rate and result in a better polymer
electrical conductivity, which induces a lower ther-
mal conductivity and thus a better figure of merit.
Figure 5 depicts the effect of varying dopant molar
concentration and reaction time with fixed oxidant
level at 0.075 mol. Conditions of 20 min of reaction
time and dopant concentration ranging from 0.009 to
0.01 mol result in a figure of merit (ZT) between
1.18 9 106 and 1.41 9 106. This result could be
related on the one hand to the fact that the figure of
3669
merit is directly influenced by the electrical conductiv-
ity, which is proportionally linked to the doping rate.
On the other hand and in terms of kinetic reaction,
20 min seems to be the optimum period allowing a
higher incorporation rate of the dopant molecule to the
polymer chain, giving a high doping level and therefore
an improved electrical conductivity.
Figure 6 presents the effect of dopant and oxidant
concentrations variation during constant reaction
time equal to 40 min. The interaction between these
two variables has generated a low value of figure of
merit (ZT) around 1.23 9 106 for molar concentra-
tion of oxidant and dopant greater than 0.09 mol.
This may be due to the prominent effect of the
reaction time, which at 40 min makes the polymer
chains creation stable with no variation, and thus
no more enhancement of conductivity at this level
time, making the impact of the two variables
become nonsignificant.
Using the model of the second-order polynomial
equation, the conducted study allowed the selection
of optimum conditions for higher figure of merit
(ZT). They are conclusively equal to 20 min for the
reaction time, 0.1 mol of oxidant and 0.005 mol of
dopant. The combination of these parameters cor-
responds to the coded factors of (1+11). At this
optimized condition, the experimental figure of
merit and its predicted value were respectively
2.71 9 106 and 2.21 9 106. Table V presents the
experimental optimum thermoelectric parameters
[Seebeck coefficient (S), electrical conductivity (r),
thermal conductivity (j), power factor (PF) involved
in the determination of figure of merit (ZT).
3670 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

Fig. 6. (a) Response surface and (b) counter plot for the figure of merit (ZT) as a function of dopant and oxidant molar concentration at a fixed
reaction time equal to 40 min.

Table V. Thermoelectric factors of polypyrrole sample prepared under the optimized variables
S (lV/K) r (S/cm) j (W/m.K) PF (W/m.K2).10210 ZT (1026) model ZT (1026)

Optimal sample 1.0672 7.538 0.0943 8.585 2.21 2.71

Table VI. Ratio of integrated absorption intensities of the 1553- and 1468-cm21 FTIR bands ðI1553 =I1468 Þ
Coded factor +1+1+1 21+121 +121+1 +1+121 212121 2121+1 +12121 21+1+1 000

I1553/I1468 2.13 1.62 2.05 1.70 2.78 1.64 1.65 1.73 1.64

Characterization compositions of various PPy samples. All the spectra

show characteristic bands at 1553 cm1 and
The goal of this part is the exploration of the
1468 cm1, indicating the extent of delocalization
relationship between polymerization conditions
in the polymer chain. These extents can be most
(model variables) selected from the optimizing pro-
easily visualized by taking the ratio of the inte-
cedures and chemical characteristics of the result-
grated absorption intensity of the 1553-cm1 band
ing polymer samples, and then correlating these
to the integrated absorption intensity of the 1468-
chemical characteristics with bulk properties
cm1 band. We note this ratio by I1553 =I1468 .
involved in the determination of thermoelectric
According to work reported by Zerbi et al.,48 the
figure of merit (ZT). To assess these chemical
I1553 =I1468 ratio is inversely proportional to the
characteristics, FTIR spectroscopy, Raman spec-
extent of delocalization (conjugation length).
troscopy and XPS have been used.
From Table VI, the spectra relative to the sample
We focuses in this study on the central part of the
with the coded factors (1+11) has shown an
studied experimental plan (axial and central
interesting value of the I1553 =I1468 ratio, reflecting
points).
the important extent of its delocalization, amongst
all the other samples. This observation is validated
FTIR Spectroscopy
by the high intensity of peaks near 1180 cm1 and
The FTIR data shown above in Fig. 3 provides a 920 cm1 describing the doping state of this sample.
wealth of information about the chemical These characteristics indicate that samples have
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties
longer chain and conjugation length inducing a
certain order degree of the polymer chain, which
makes the carrier mobility easier. Consequently,
this sample of PPy will have an improved electrical
conductivity and Seebeck coefficient, as they are
dependent on the carrier mobility and, thus, a
remarkable improvement in the figure of merit (ZT).
Raman Spectroscopy
In order to gain more insight on the effect of the
polymerization conditions on thermoelectric prop-
erties, samples were characterized by Raman spec-
troscopy and the results are presented in Fig. 7.
All samples display two noticeable peaks located at
1358 cm1 and 1570 cm1, related to the pyrrole
ring and the C=C molecular chain stretching
vibration of PPy, respectively. Calculation of the
peak’s intensity ratio (I1358/I1570) is given in
Table VII.
Comparatively, it can be seen that the peak
intensity ratio of (I1358/I1570) shown by the sample
designed by the coded factor of (1+11) is signif-
icantly reduced, which is an indication on the
enhancement of the conjugated structure, the
increase of the order degree in the molecular chain,
and the decrease of the defect degree in this sample.
Both of these features contributed to facilitate the
Fig. 7. Raman spectra of the prepared polypyrrole samples
according their coded factors. (Unit normalization is done by
changing the range of intensity values, where the maximum values
in each spectrum is equal to one).
Table VII. Ratio of integrated absorption intensities of the 1570- and 1358-cm21 Raman bands ðI1358 =I1570 Þ
Coded factor +1+1+1 21+121 +121+1 +1+121
I1358/I1570 0.79 0.65 0.81 0.80
3671
charge carrier mobility, which has a direct impact
on the increase of the electronic conductivity and
Seebeck coefficient, and thus the figure of merit (ZT)
value is increased.
XPS Spectroscopy
For further elucidation of the influence of the
studied variables on the doping level and the
electronic bulk properties, XPS was carried for the
sample that has shown the highest value of figure of
merit (ZT). Results depicted in Fig. 8a display the
XPS survey spectra for PPy; it shows five prominent
peaks: S2p ( 168 eV), Cl2p doublet centered at
198.3–200.4 eV, C1s centered at ( 285 eV), N1s
centered at (400 eV), and O1s at ( 533 eV). In
order to obtain information about doping level, high-
resolution N1s spectra were recorded and presented
on Fig. 8b. The ratio of positively charge nitrogen
(N+) is the sum of –NH+-polaron and =NH+-bipo-
laron, with the neutral nitrogen corresponding to
amine; this gives a doping level of 40.61%. As the
doping level is proportional to the conjugation and
chain length, the obtained value suggests that
conjugation/chain length are considerable in this
optimized PPy sample. Such doping level permits
the sample to improve in terms of conductivity and
Seebeck coefficient and, hence, this could explain
the higher value of figure of merit (ZT) obtained
with this sample.
SEM Characterization
The optimized sample having the coded factor
(1+11) was imaged by SEM to observe its mor-
phology. As shown in Fig. 9, the morphology of the
final product strongly depends on the oxidant type,
its concentration and the reaction time, and the
application of FeCl3 in this study and its optimized
concentration within the short time of 20 min has led
to a scale-like shape, or as more commonly known, a
cauliflower-like shape, made up of small granular
particles. The obtained shape could be the good form
of morphology that contributes to improved conduc-
tivity and Seebeck coefficient.
THE RELATIONSHIP BETWEEN
FIGURE OF MERIT (ZT)
AND TEMPERATURE
Figure 10 shows the temperature dependence of
figure of merit (ZT) over the range 293–373 K, for
the optimized PPy sample. ZT enhances with
212121 2121+1 +12121 21+1+1 000
0.77 0.72 0.88 0.78 0.77
3672
Fig. 8. (a) Polypyrrole XPS survey scan: (b) N1s high resolution spectra of polypyrrole sample.
increasing temperature. The ZT of  5.86 9 105
exhibited at 373 K is 22 times higher compared to
its value found at 273 K. As noticed on Table VIII,
this result derives from the improvement of both
electrical conductivity (r) and Seebeck coefficient
(S), which reach their higher value at 373 k, and
from the reduced thermal conductivity (j) evolution
within the applied temperature range. In fact,
increasing the temperature slows down the thermal
conductivity (j) along with a proportional increase
Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti
of electrical conductivity (r) and Seebeck coefficient;
this resulted in an improved thermoelectric perfor-
mance of optimized PPy.
THERMOELECTRIC PROPERTIES COM-
PARISON
Although there are few works dealt with deter-
mination of PPy thermoelectric properties at room
temperature, it can be seen from Table VIII that
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped 3673
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties

Fig. 9. SEM images (a) and (b) of different sites from optimized polypyrrole sample.

various other reported PPy samples and their

composites show relatively similar power factor
and figure of merit values even at high temperature,
compared to values found within the present work.

Fig. 10. Temperature dependence of figure of merit (ZT).
CONCLUSION
For the development of conducting polymers in
the field of thermoelectric applications, it is neces-
sary to find an approach and conditions that allow
obtaining easily a stable polymer with high conduc-
tivity, high Seebeck coefficient and, consequently,
high figure of merit (ZT). Accordingly, we examined
optimization of PPy chemical synthesis in aqueous
solution with an organic sulfonic acid dopant by
using RSM based on CCD. In fact, PPy chemical
synthesis was optimized using three variables (re-
action time, oxidant and dopant molar concentra-
tion) for a maximum figure of merit (ZT) considered

Table VIII. Comparison of thermoelectric properties of polypyrrole samples of this work with ones found in
the literature
Work
temperature Year
Sample (material) S (lV/K) r (S/cm) j (W/m K) PF (W/m K2) ZT (K) (ref.)

PPy 1.07 7.54 0.0943 8.59 9 1010 2.71 9 106 298 This work
PPy 7.30 7.19 – 0.038 9 106 – 363 2017a
PPy – – – 0.0376 9 106 – 363 2014b
PPy 16.5 11.6 0.12 0.32 9 106 1.01 9 103 380 2017c
PPy–NT/paper 5.34 0.048 0.1275 1.37 9 1010 0.32 9 106 300 2017d
nanocomposite films
a
Wang et al.49
b
Wang et al.50
c
Misra et al.51
d
Li et al.52
3674
as the response methodology. A second-order poly-
nomial model was acceptable to develop the corre-
lation between independent and dependent
variables. ANOVA results show good agreement
between experimental and predicted responses, as
given by a high R2 value of 0.83. Response surface
plots revealed on the one hand the matching trend
of oxidant and dopant concentrations with the
response (ZT) by offering more sites on the polymer
chain for a high doping rate. On the other hand, it
showed the opposite trend of reaction time to the
response, which is related to the chain length
stability and its order degree reached by the poly-
mer above a defined time reaction. Numerical
optimization and validation of the optimized syn-
thesis conditions of PPy showed good predictability
of the model employed for response.
The application of this procedure has demon-
strated that the chemical characteristics and the
bulk properties of samples [electronic conductivity
(r), Seebeck coefficient (S) and thermal conductivity
(j)] are highly dependent on the synthesis condi-
tions. Furthermore, spectroscopy and morphology
characterizations were used to correlate chemical
characteristics with electronic properties; they
reveal that considered variables play a dominant
role in the enhancement of molecular chain ordering
and conjugation length, leading to an improved
figure of merit (ZT). These results highlight the
possibility of conceiving a promising organic mate-
rial based on conducting polymer with favorable
qualities for efficient thermoelectric properties.
Moreover, considering the paramount role of the
ZT in ranking good thermoelectric materials, and
therefore the efficiency of conversion from heat into
electricity, it is thus important to measure it
accurately. Hence, it is very important to think
through the future work to corroborate the obtained
values by using a ZT meter.
ACKNOWLEDGMENTS
Zakaria BDS. wishes to thank Ecole Militaire
Polytechnique and Université Paris-Est, Centre
d’Etudes et de Recherche en Thermique Environ-
nement et Systèmes (CERTES), for a provision of
scholarship within the framework of an Algerian-
French co-tutelle PhD program granted under the
project number N01/16/DRFPG/CMDT.
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