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:
[email protected]. 4.—e-mail: [email protected]

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
countries over recent years, causing the fast
Nowadays, reports on energy forecasts are alarm- decrease of energy reserves and the high cost for
ing in regard to the lack of worldwide conventional exploration of new technologies.1 With a similar
energy resources. Particularly, statistical studies 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
(Received November 16, 2018; accepted March 8, 2019;
published online March 20, 2019) production process based on photovoltaics,2,3 fuel

3662
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped 3663
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties

cells,4 wind turbines,5 and biomass.6,7 In recent applications related to the anti-electrostatic coat-
years, thermoelectricity has appeared as a promis- ings,27 batteries,28 sensors29–31 …etc.
ing alternative.8,9 It offers a way to convert waste Moreover, the efficiency of PPy depends largely on
heat energy into electrical power,10,11 based on the the competition of multiple factors.32 Indeed, many
Seebeck effect. Semiconductor compounds like works highlight the effect of the material doping
Si1x Gex alloys, half-Heusler compounds, skutteru- level33 on conductivity values. However, they have
dites and tellurides like Bi2 Ti3 and PbTe are omitted the important influence of reaction time,
recognized to be the best materials,12 based on their and the interaction effect of both oxidant and
efficiency. Generally, the thermoelectric efficiency is dopant concentrations, which have not been stated
quantified by dimension-less thermoelectric figure of elsewhere. Optimization of significant influencing
merit,13,14 defined as: factors on the thermoelectric behavior of polymers is
of great interest. Some attempts emphasize the
S2 r contribution from the monomer concentration, and
ZT ¼ T ð1Þ the polymer morphologies.34 However, studying
j
such variable parameters requires considerable
where S, r, j, and T are respectively the Seebeck quantity of raw material and is time-consuming.
coefficient, the electrical conductivity, the isother- Thus, researchers are making recourse to the
mal conductivity and the absolute temperature. optimization technique,35 in order to overcome these
Since the 1990s, a large number of researches have hindrances.36 Response surface methodology (RSM)
been conducted aiming at enhancing the thermo- is widely used for experimental design and opti-
electric efficiency of inorganic material, through mization processes, via combining mathematical
improving the Seebeck coefficient and reducing modeling and statistical techniques.37–39 It is con-
thermal conductivity by increasing the scattering sidered as the faster and less laborious technique,
of phonons.15 These efforts have put forward the requiring minimum experimental procedures for
significant role of geometry optimization and reduc- optimization of multiple independent variables.
tion of the physical dimensionality of the material. The shortcoming of detailed information regard-
Although significant improvement has been made, ing the enhancement of thermoelectric perfor-
the conversion efficiency of thermal energy to mances of conducting polymers, based on the
electrical energy is still lower than the maximum consideration of their synthesis parameters, has
required by Carnot efficiency.16 Moreover, the pro- motived the present study. We report in this study a
gress of inorganic materials has not realized any synthesis procedure based on RSM and reduced
increase because of their expensive cost, scarcity number of experimental runs, aiming at evaluating
and/or toxicity, and the difficulty of their the relationship between the effect of different
processing.17 pyrrole polymerization parameters taken alone
Lately, another important category of thermoelec- and the resulting thermoelectric figure of merit
tric materials mainly includes organic material- (ZT), therewith considering also the interaction
based conducting polymers (CPs) and their compos- effects among the independent parameters. There-
ites; these compounds have experienced a rapid after, the chemical characteristics of optimized PPy
ascension,18 making them potential candidates sub- were correlated with its measured bulk properties
stituting for inorganic materials. This class of (electrical conductivity and Seebeck coefficient) by
materials present versatile advantages, such as several techniques such as Fourier transform infra-
the raw materials’ availability, lack of toxicity, red (FTIR) spectroscopy, Raman spectroscopy, x-ray
solution treatment, good flexibility, low cost, light- photoelectron spectroscopy (XPS) and scanning
weight, adjustable molecular structure and low electron microscopy (SEM). The entire, selected
thermal conductivity (j).19 In addition to these synthesis parameters have proven to be effective
characteristics, another factor known as power for reaching precisely the aimed thermoelectric
factor (PF) estimated by the multiplication product performances.
of (S2r) is used to replace the figure of merit (ZT) for
the thermoelectric performance assessment. Several EXPERIMENT
intrinsically conducting polymers (ICPs) demon-
Materials and Methods
strated a significant enhancement in their thermo-
electric properties, via their increase in the figure of Pyrrole (purchased from Sigma-Aldrich, purity >
merit by orders of magnitude, reaching values close 98%) was subjected to distillation under reduced
to those of inorganic materials.20 pressure and then stored at 4C in the dark prior to
To date, the main conducting polymers applied as synthesis. Dodecylbenzene sulfonic acid (supplied
thermoelectric materials are, poly(3,4-ethylene- by Sigma-Aldrich, purity > 98%) and iron chloride
dioxythiophene) (PEDOT), polyaniline (PANI),21 hexahydrate were used as received. Organic sol-
polypyrrole (PPy)22 and polythiophene (PTH).23,24 vents were of analytical grade. Deionized (DI) water
Amongst all of them, PPy affords promising char- was used throughout the synthesis steps for solu-
acteristics,25,26 which broadens its usage in other tion preparation and washing.
3664 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

Characterization and Thermoelectric Perfor- pellets by cold-pressing the powder samples at

mances Determination 20 MPa.
Raman spectroscopy was carried out using a
The electrical conductivity (r) was measured
Thermo-Fisher DXR 2 spectrometer; excitation
using the conventional four-probes technique with
was at 532 nm from a He–Ne laser at room tem-
a Jandel RM 3000 (with typical probe separation of
perature. Fourier transform infrared (FTIR) spectra
1 mm).
were collected in attenuated total reflection (ATR)
Thermal conductivity (j) was determined using
mode in the wave number range 4000–600 cm1
the hot-disc 2500S method according to the stan-
with a nominal resolution of 4 cm1 over 50 scans,
dard test method. This method is valid for measur-
using a Perkin Elmer 100 spectrometer. Sample
ing thermal conductivities of polymeric materials
morphology was observed using an FEI-Quanta 600
with values within the range 0.1–1 W.m1.k1. The
scanning electron microscope under an acceleration
Seebeck coefficient was determined using a home-
voltage of 15 kV and at a working distance of 14 nm.
made apparatus (see Fig. 1), wherein the tempera-
Elementary composition analysis was determined
ture was determined using embedded
using x-ray photoelectron spectroscopy (XPS,
thermocouples in a heating cartridge controlled by
Thermo Scientific ESCALAB 250Xi).
supplied stabilized current, and a Keithley multi-
meter/switching system; the cooling system was
Polypyrrole Synthesis and Statistical Analysis
ensured by the circulation of cold water through a
Design
copper coil and using an RS 360 water pump. In
order to obtain precise values, the apparatus was As shown in Fig. 2, the chemical oxidative method
subject of validation procedures conducted on cop- was used for the PPy synthesis. In typical synthesis
per plates samples with known values. The Seebeck procedures, 100 mL of dodecylbenzene sulfonic acid
coefficient is the slope of linear regression of elec- aqueous solution is mixed with a solution of iron
trical potential DV, as a function of temperature, chloride hexahydrate dissolved in 100 ml of DI
DT  10 K, and is given by the following equation: water. Then, the obtained mixture was kept under
magnetic stirring for 15 min at a temperature of 0
DV C. Subsequently, we added dropwise a precooled
S¼ ð2Þ
DT solution of 0.1 mol of pyrrole monomer to the
previous solution, kept under stirring during differ-
For thermoelectric measurements (electrical con- ent reaction times, allowing the polymerization
ductivity and Seebeck coefficient), a hydraulic press reaction to proceed. Finally, filtration of resulting
and homemade mold were used to prepare PPy black precipitate was performed, followed by rinsing

Fig. 1. Schematic presentation of homemade apparatus for Seebeck coefficient measurement.

Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped 3665
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 from different sides, through which several
solution was colorless. The resulting product was researchers have considered the oxidant, the dopant
dried under vacuum at 80C for 8 h. Upon collecting and the polymerization time effect on the reaction
each sample, FTIR and Raman spectroscopy anal- efficiency and the electrical conductivity of the
yses were carried out in order to characterize the material. Studies were conducted for molar ratios
obtained product structure. of oxidant/monomer ranging between 1:1 and
In order to obtain optimized thermoelectric prop- 1:6,40,41 or molar ratios of dopant/monomer varied
erties of PPy, the synthesis PPy conditions were between 1:10 and 1:25,42,43 and for a polymerization
followed by employing central composite design time up to 24 h.27,40,44
(CCD) techniques, which considers an independent The formulated experimental design was based on
variables packet. The reaction time (T), oxidant CCD with a total number of treatment combinations:
concentration (O) and dopant concentration (D) are
the input variables, and their levels and ranges N ¼ 2k þ 2k þ nc : ð3Þ
were set as follows: reaction time was varied from
20 to 60 min, oxidant concentration was taken at where k is the number of treatment factors (k = 3),
three different values (0.05, 0.075 and 0.1) and nc is the replicates number of treatment combina-
dopant concentration was equal to 0.005, 0.0075 and tions at the center (nc = 6), which are very neces-
0.01). sary for the estimation of ‘‘pure error.’’ And 2 is the
Aiming to produce a polymer with an optimal number of axial points in the axis of each treatment
conductivity and, consequently, an important ther- factor, at a distance of a (a = 2(k/4) = 2(3/4) = 1.682)
moelectric effect, the choice of our experimental from the design center.45 The coded and actual
design was based on results obtained in earlier factors used for this experiment are given in
work. In fact, the synthesis of PPy has been studied 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 Moreover, multiple regression analysis, analysis
total number of 20 experiments [N = 23 + of variance (ANOVA for response surface reduced
(2 9 3) + 6 = 20] and analyze the experimental cubic model), and determination of coefficient R2 for
data. the estimation of the model fit regression were done
The standard and run orders, variable factors, by using the same software, Design Expert. The
determined figure of merit (ZT) and its predicted total error criteria with a confidence level of 95%
values are shown on Table II. were the basis for statistical test significance.
The mathematical relationship between the inde- Table II lists the run order, variables factors,
pendent variables and the obtained responses in determined figure of merit (ZT) and its predicted
terms of figure of merit (ZT), were established by values.
fitting the experimental data to a second-order
polynomial equation as given by: RESULTS AND DISCUSSION
X X XX
Y ¼ b0 þ b i Xi þ Bii Xi2 þ bij Xi Xj ð4Þ As shown in Fig. 3, FTIR spectra of PPy samples
(obtained by the combination of different reaction
where Y is the response variable, b0 is the constant, times, varied molar concentrations of oxidant, and
and bi, bii and bij represent the linear, quadratic varied molar concentrations of dopant) are almost
and interactive coefficient, respectively. Xi and Xj the same, suggesting the same molecular structure.
represent the independent variables. 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- predict model for the figure of merit (ZT) based on
metric and antisymmetric elongation of the pyrrole second-order polynomial equation are listed in
cycle. Table IV. Values of (P < 0.05) indicate that both
Table III summarizes room temperature mea- effects rising from reaction time, oxidant molar
surements of electrical conductivity and thermo- concentration and dopant molar concentration on
electric properties (thermal conductivity and the figure of merit ZT are significant.
Seebeck coefficient) of samples. The regression coefficients R2 of 0.83 indicate that
the regressed model of figure of merit ZT is accept-
Model Analysis able and corresponds to the experimental results.
Furthermore, application of the regression model
The multiple regression coefficients obtained by
found for the figure of merit permits the comparison
the application of least squares technique in order to
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
Fig. 3. FTIR spectra of prepared PPy samples according to their IV, we reveal a P value of 0.0075, which indicates
coded factors. (Unit normalization is done by changing the range of that the model is highly significant. There is only
intensity values, where the maximum values is in each spectrum is 0.75% chance that a ‘‘lack of fit F-value’’ occurs due
equal to one).
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 The analysis of a three-dimensional response
(0.01 < P < 0.05) indicates that the reaction time, surface graph and a two-dimensional contour
the oxidant’s molar concentration and the dopant plotted from the linear, quadratic and the inter-
concentration had significant effect the on figure of action terms of the determined second-order
merit ZT, and signify that X1, X2, X3, X21, X22 and X23 polynomial model is used to select the maxi-
are significant model terms. mum, minimum and saddle points of the
Regarding the interaction effects study, either response, and evaluate the variables’ impact on
considering single parameters or a number of the response. It helps to observe interactions
assembled parameters, it is deduced from P values between two factors by holding the third one
(P > 0.05) that the interactions between the reac- constant at its considered center level. However,
tion time and the oxidant’s molar concentration, it is found out that only the two-dimensional
oxidant’s molar concentration and dopant molar plot is more suitable for the determination of the
concentration, and reaction time within the exper- responsibility degree of each variable on the
imental range, were not significant. 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 3669
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 merit is directly influenced by the electrical conductiv-
surface of the oxidant’s molar concentration and the ity, which is proportionally linked to the doping rate.
reaction time effect on the figure of merit, at a fixed On the other hand and in terms of kinetic reaction,
dopant molar concentration equal to 0.01 mol. The 20 min seems to be the optimum period allowing a
improved values of figure of merit (ZT) around higher incorporation rate of the dopant molecule to the
1.63 9 106 until 1.94 9 106 are observed at a polymer chain, giving a high doping level and therefore
reaction time of 20 min and an oxidant concentra- an improved electrical conductivity.
tion included between 0.09 and 0.1 mol. These Figure 6 presents the effect of dopant and oxidant
observations are possibly due to: (1) the pyrrole concentrations variation during constant reaction
polymerization rate is related to the concentration time equal to 40 min. The interaction between these
of the oxidant, and it could be increased by the two variables has generated a low value of figure of
addition of an excess of oxidant, according to merit (ZT) around 1.23 9 106 for molar concentra-
previous study.46 At such concentration, the pres- tion of oxidant and dopant greater than 0.09 mol.
ence of oxidant anions is essential for the way in This may be due to the prominent effect of the
which the doping species will be incorporated into reaction time, which at 40 min makes the polymer
the polymer instead of the oxidant anions, and chains creation stable with no variation, and thus
hence it will determine its good conductivity and no more enhancement of conductivity at this level
stability. (2) According to pyrrole polymerization time, making the impact of the two variables
kinetics,47 it seems that within an equilibrium become nonsignificant.
reaction time around 20 min and the optimum Using the model of the second-order polynomial
oxidant concentration, pyrrole polymerization equation, the conducted study allowed the selection
reached its high mass quantity. (3) The combination of optimum conditions for higher figure of merit
of the two cited conditions affect the pyrrole poly- (ZT). They are conclusively equal to 20 min for the
merization rate and result in a better polymer reaction time, 0.1 mol of oxidant and 0.005 mol of
electrical conductivity, which induces a lower ther- dopant. The combination of these parameters cor-
mal conductivity and thus a better figure of merit. responds to the coded factors of (1+11). At this
Figure 5 depicts the effect of varying dopant molar optimized condition, the experimental figure of
concentration and reaction time with fixed oxidant merit and its predicted value were respectively
level at 0.075 mol. Conditions of 20 min of reaction 2.71 9 106 and 2.21 9 106. Table V presents the
time and dopant concentration ranging from 0.009 to experimental optimum thermoelectric parameters
0.01 mol result in a figure of merit (ZT) between [Seebeck coefficient (S), electrical conductivity (r),
1.18 9 106 and 1.41 9 106. This result could be thermal conductivity (j), power factor (PF) involved
related on the one hand to the fact that the figure of 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 3671
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties

longer chain and conjugation length inducing a charge carrier mobility, which has a direct impact
certain order degree of the polymer chain, which on the increase of the electronic conductivity and
makes the carrier mobility easier. Consequently, Seebeck coefficient, and thus the figure of merit (ZT)
this sample of PPy will have an improved electrical value is increased.
conductivity and Seebeck coefficient, as they are
dependent on the carrier mobility and, thus, a XPS Spectroscopy
remarkable improvement in the figure of merit (ZT).
For further elucidation of the influence of the
studied variables on the doping level and the
Raman Spectroscopy
electronic bulk properties, XPS was carried for the
In order to gain more insight on the effect of the sample that has shown the highest value of figure of
polymerization conditions on thermoelectric prop- merit (ZT). Results depicted in Fig. 8a display the
erties, samples were characterized by Raman spec- XPS survey spectra for PPy; it shows five prominent
troscopy and the results are presented in Fig. 7. peaks: S2p ( 168 eV), Cl2p doublet centered at
All samples display two noticeable peaks located at 198.3–200.4 eV, C1s centered at ( 285 eV), N1s
1358 cm1 and 1570 cm1, related to the pyrrole centered at (400 eV), and O1s at ( 533 eV). In
ring and the C=C molecular chain stretching order to obtain information about doping level, high-
vibration of PPy, respectively. Calculation of the resolution N1s spectra were recorded and presented
peak’s intensity ratio (I1358/I1570) is given in on Fig. 8b. The ratio of positively charge nitrogen
Table VII. (N+) is the sum of –NH+-polaron and =NH+-bipo-
Comparatively, it can be seen that the peak laron, with the neutral nitrogen corresponding to
intensity ratio of (I1358/I1570) shown by the sample amine; this gives a doping level of 40.61%. As the
designed by the coded factor of (1+11) is signif- doping level is proportional to the conjugation and
icantly reduced, which is an indication on the chain length, the obtained value suggests that
enhancement of the conjugated structure, the conjugation/chain length are considerable in this
increase of the order degree in the molecular chain, optimized PPy sample. Such doping level permits
and the decrease of the defect degree in this sample. the sample to improve in terms of conductivity and
Both of these features contributed to facilitate the 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
Fig. 7. Raman spectra of the prepared polypyrrole samples
according their coded factors. (Unit normalization is done by Figure 10 shows the temperature dependence of
changing the range of intensity values, where the maximum values
in each spectrum is equal to one).
figure of merit (ZT) over the range 293–373 K, for
the optimized PPy sample. ZT enhances with

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 212121 2121+1 +12121 21+1+1 000

I1358/I1570 0.79 0.65 0.81 0.80 0.77 0.72 0.88 0.78 0.77
3672 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

Fig. 8. (a) Polypyrrole XPS survey scan: (b) N1s high resolution spectra of polypyrrole sample.

increasing temperature. The ZT of  5.86 9 105 of electrical conductivity (r) and Seebeck coefficient;
exhibited at 373 K is 22 times higher compared to this resulted in an improved thermoelectric perfor-
its value found at 273 K. As noticed on Table VIII, mance of optimized PPy.
this result derives from the improvement of both
electrical conductivity (r) and Seebeck coefficient
THERMOELECTRIC PROPERTIES COM-
(S), which reach their higher value at 373 k, and
PARISON
from the reduced thermal conductivity (j) evolution
within the applied temperature range. In fact, Although there are few works dealt with deter-
increasing the temperature slows down the thermal mination of PPy thermoelectric properties at room
conductivity (j) along with a proportional increase 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.

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-
Fig. 10. Temperature dependence of figure of merit (ZT). 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 Bekkar Djelloul Sayah, Mekki, Delaleux, Riou, and Durastanti

as the response methodology. A second-order poly- 6. N.L. Panwar, S.C. Kaushik, and S. Kothari, Renew. Sustain.
nomial model was acceptable to develop the corre- Energy Rev. 15, 1513 (2011).
7. A. Demirbas, Progress Energy Combust. Sci. 31, 171 (2005).
lation between independent and dependent 8. L.E. Bell, Science 321, 1457 (2008).
variables. ANOVA results show good agreement 9. B.I. Ismail and W.H. Ahmed, Electr. Electron. Eng. 2, 27
between experimental and predicted responses, as (2009).
given by a high R2 value of 0.83. Response surface 10. S.B. Riffat and X. Ma, Appl. Therm. Eng. 23, 913 (2003).
11. C.T. Hsu, G.Y. Huang, H.S. Chu, B. Yu, and D.J. Yao, Appl.
plots revealed on the one hand the matching trend Energy 88, 1291 (2011).
of oxidant and dopant concentrations with the 12. C. Han, Z. Li, and S. Dou, Chin. Sci. Bull. 59, 2073 (2014).
response (ZT) by offering more sites on the polymer 13. E. Li, N. Wang, H. He, and H. Chen, Nanoscale. Res. Let. 11,
chain for a high doping rate. On the other hand, it 188 (2016).
showed the opposite trend of reaction time to the 14. J. Kangsabanik and A. Alam, J. Mater. Chem. A 5, 6131
(2017).
response, which is related to the chain length 15. Q. Zhang, X. Ai, L. Wang, Y. Chang, W. Luo, W. Jiang, and
stability and its order degree reached by the poly- L. Chen, Adv. Funct. Mater. 25, 966 (2015).
mer above a defined time reaction. Numerical 16. H. Zhu, R. He, J. Mao, Q. Zhu, C. Li, J. Sun, W. Ren, Y.
optimization and validation of the optimized syn- Wang, Z. Liu, Z. Tang, A. Sotnikov, Z. Wang, D. Broido, D.J.
Singh, G. Chen, K. Nielsch, and Z. Ren, Nat. Commun. 9,
thesis conditions of PPy showed good predictability 2497 (2018).
of the model employed for response. 17. C. Ou, A.L. Sangle, A. Datta, Q. Jing, T. Busolo, T. Chalk-
The application of this procedure has demon- len, V. Narayan, and S. Kar-Narayan, ACS. Appl. Mater
strated that the chemical characteristics and the Interface 10, 19580 (2018).
bulk properties of samples [electronic conductivity 18. S. Peng, D. Wang, J. Lu, M. He, C. Xu, Y. Li, and S. Zhu, J.
Polym. Environ. 25, 1208 (2017).
(r), Seebeck coefficient (S) and thermal conductivity 19. W. He, G. Zhang, X. Zhang, J. Ji, G. Li, and X. Zhao, Appl.
(j)] are highly dependent on the synthesis condi- Energy 13, 1 (2015).
tions. Furthermore, spectroscopy and morphology 20. J. Zhao, D. Tan, and G. Che, J. Mater. Chem. 5, 47 (2017).
characterizations were used to correlate chemical 21. J. Wu, Y. Sun, W. Xu, and Q. Zhang, Synth. Met. 189, 177
(2014).
characteristics with electronic properties; they 22. J. Wu, Y. Sun, W.B. Pei, L. Huang, W. Xu, and Q. Zhang,
reveal that considered variables play a dominant Synth. Met. 196, 173 (2014).
role in the enhancement of molecular chain ordering 23. C. Gao and G. Chen, Compos. Sci. Technol. 124, 52 (2016).
and conjugation length, leading to an improved 24. X. Hu, G. Chen, and X. Wang, Compos. Sci. Technol. 144, 43
figure of merit (ZT). These results highlight the (2017).
25. I. Shown, A. Ganguly, L.C. Chen, and K.H. Chen, Energy
possibility of conceiving a promising organic mate- Sci. Eng. 3, 2 (2015).
rial based on conducting polymer with favorable 26. R. Kroon, D.A. Mengistie, D. Kiefer, J. Handymen, J.D.
qualities for efficient thermoelectric properties. Ryan, L. Yu, and C. Müller, Chem. Soc. 45, 6147 (2016).
Moreover, considering the paramount role of the 27. L. Liang, G. Chen, and C.Y. Guo, Mater. Chem. Front. 1, 380
(2017).
ZT in ranking good thermoelectric materials, and 28. D. Su, J. Zhang, S. Dou, and G. Wang, Chem. Commun. 51,
therefore the efficiency of conversion from heat into 16092 (2015).
electricity, it is thus important to measure it 29. T.F. Otero and S. Beaumont, Sens. Actuators B 253, 958
accurately. Hence, it is very important to think (2017).
through the future work to corroborate the obtained 30. B. Mettai, A. Mekki, F. Merdj, Z. Bekkar Djelloul Sayah, K.
Moustefai Soumia, Z. Safiddine, R. Mahmoud, and M.M.
values by using a ZT meter. Chehimi, J. Polym. Res. 25, 95 (2018).
31. F. Merdj, A. Mekki, D. Guettiche, B. Mettai, Z. Bekkar
Djelloul Sayah, Z. Safidine, A. Abdi, R. Mahmoud, and M.M.
ACKNOWLEDGMENTS Chehimi, Macromol. Res. 26, 511 (2018).
32. L. Liang, G. Chen, and C.Y. Guo, Compos. Sci. Technol. 129,
Zakaria BDS. wishes to thank Ecole Militaire 130 (2016).
Polytechnique and Université Paris-Est, Centre 33. Q. Zhang, Y. Sun, W. Xu, and D. Zhu, Adv. Mater. 26, 6829
d’Etudes et de Recherche en Thermique Environ- (2014).
nement et Systèmes (CERTES), for a provision of 34. Y. Li, Y. Du, Y. Dou, K. Cai, and J. Xu, Synth. Met. 226, 119
scholarship within the framework of an Algerian- (2017).
35. J.V.D. Perez, E.T. Nadres, H.N. Nguyen, M.L.P. Dalida, and
French co-tutelle PhD program granted under the D.F. Rodrigues, RSC Adv. 7, 18480 (2017).
project number N01/16/DRFPG/CMDT. 36. M. Saad, H. Tahir, J. Khan, U. Hameed, and A. Saud, Ul-
trason. Sonochem. 34, 600 (2017).
REFERENCES 37. I. Mangilia, M. Lasagnia, K. Huangb, and A.I. Isayevb,
1. J. Ongena and G.V. Oost, Fusion Sci. Technol. 61, 3 (2012). Chemom. Intell. Lab. Syst. 144, 1 (2015).
2. P.O. Logerais, O. Riou, M.A. Camara, and J.F. Durastanti, 38. M.A. Bezerra, R.E. Santelli, E.P. Oliveira, L.S. Villar, and
J. Solar Energy 2013, 1 (2013). L.A. Escaleira, Talanta 76, 965 (2008).
3. N. Wang, T. Ding, W. Liu, A.S. Ahmed, Z. Wang, M. Tian, 39. M. Rahmani, E. Ghasemi, and M. Sasani, Talanta 165, 27
X.W. Sun, and Q. Zhang, Adv. Energy Mater. 7, 1700522 (2017).
(2017). 40. A. Yussuf, M. Al-Saleh, S. Al-Enezi, and G. Abraham, Int. J.
4. R.B. Song, Y.C. Wu, Z.Q. Lin, J. Xie, C.H. Tan, J.S.C. Loo, B. Polym. Sci. 2008, 8 (2018).
Cao, J.R. Zhang, J.J. Zhu, and Q. Zhang, Angew. Chem. Int. 41. J.Y. Leea, K.T. Songb, S.Y. Kimb, Y.C. Kim, D.Y. Kima, and
Ed. 56, 10516 (2017). C.Y. Kima, Synth. Met. 84, 137 (1997).
5. H. Yang, Z. Wei, and L. Chengzhi, Appl. Energy 86, 163 42. L.X. Wang, X.G. Li, and Y.L. Yang, React. Funct. Polym. 45,
(2009). 125 (2001).
Response Surface Methodology as a Powerful Tool for the Synthesis of Polypyrrole-Doped 3675
Organic Sulfonic Acid and the Optimization of Its Thermoelectric Properties
43. K. Chatterjee, S. Ganguly, K. Kargupta, and D. Banerjee, 49. Y. Wang, J. Yang, L. Wang, K. Du, and Q. Yin, ACS Appl.
Synth. Met. 161, 275 (2011). Mater. Interfaces 9, 20124 (2017).
44. S. Bahraeian, K. Abron, F. Pourjafarian, and R.A. Majid, 50. L.Y. Wang, F.Z. Liu, C. Jin, T.R. Zhang, and Q.J. Yin, RSC
Adv. Mat. Res. 795, 707 (2013). Adv. 4, 46187 (2014).
45. D.C. Montgomery, Design and Analysis of Experiments 51. S. Misra, M.B. Harti, A. Singh, D.K. Aswal, and Y. Haya-
(New York: Wiley, 2017). kawa, Mater. Res. Express 4, 085007 (2017).
46. F. Ferrero, L. Napoli, C. Tonin, and A. Varesano, J. Appl. 52. J. Li, Y. Du, R. Jia, J. Xu, and S.Z. Shen, Coatings 7, 211
Polym. Sci. 102, 4121 (2006). (2017).
47. M.F. Planche, J.C. Thleblemont, N. Mazars, and C. Bidan,
J. Appl. Polym. Sci. 52, 1867 (1994). Publisher’s Note Springer Nature remains neutral with
48. G. Zerbi, C. Castiglioni, J.T. Lopez Navarrete, B. Tian, and regard to jurisdictional claims in published maps and institu-
M. Gussoni, Synth. Met. 28, D359 (1989). tional affiliations.
Reproduced with permission of copyright owner. Further reproduction
prohibited without permission.