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Thermal and dielectric behavior of polyamide-6/clay nanocomposites

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 Materials Chemistry and Physics 232 (2019) 99–108

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Thermal and dielectric behavior of polyamide-6/clay nanocomposites

Imen Hammami a, *, Helmi Hammami a, J�er�emie Soulestin b, Mourad Arous a, Ali Kallel a
a
LaMaCoP, Faculty of Sciences of Sfax, Department of Physic, University of Sfax, 3018, Sfax, Tunisia
b
TPCIM, IMT Lille Douai, Department of Polymers and Composites Technology and Mechanical Engineering, University of Lille, 59500, Douai, France

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

Keywords: In this work, the influence of the incorporation of nanoparticles (organo-modified montmorillonite Cloisite 30B)
Polymer in polyamide 6 (PA6) on rigid amorphous fraction (RAF) formation had been explored employing Differential
Composite Scanning Calorimetry (DSC), Flash Differential Scanning Calorimetry (Flash DSC) and Broadband Dielectric
Interface
Spectroscopy (BDS) techniques. The existence of a RAF in PA6-montmorillonite nanocomposite films is available
from specific heat capacity measurement at the glass transition region of the nanocomposites. It was shown that
at high C30B content, this fraction becomes larger. Using Flash DSC, it was possible not only to measure the heat
capacity step at the glass transition of the materials, but also to provide quantitative knowledge on the kinetics of
crystallization and nucleation of PA6-based nanocomposites. The dielectric relaxation spectroscopy measure­
ment was investigated, in the frequency range 0.1–106 Hz and varying temperature from 20 to 200 � C, which
highlight different relaxation phenomena: the α dipolar relaxation, the αc relaxation and Max­
well–Wagner–Sillars (MWS) interfacial polarizations. As C30B content increases, a MWS relaxation emerges in
the nanocomposites, thus revealing the increase of RAF in the nanocomposite with high C30B content.

1. Introduction balance cost/performance [2]. The presence of clay nanoparticles in the

Polymer nanocomposites have attracted a great deal of attention in
recent years due to their exceptional properties. Indeed, filling polymers
with nanoparticles, particularly those containing high aspect ratio
nanofillers, is used to enhance physical characteristics, such as increased
mechanical strength, resistance to dielectric breakdown, and improved
thermal behavior [1].
Among the Numerous types of nanosized fillers, clay and layered
silicates are the most commonly used nanofiller because of their natural
abundance, their low cost and their high aspect ratio (greater than 100).
To optimize and to control the montmorillonite (MMT) filled nano­
composites performance, it is essential to increase as much as possible
the degree of nanoparticles exfoliation and dispersion within polymer
matrix for creating large interaction surfaces promoting the formation of
interphase. These interphases are formed due to the existence of an
amorphous polymer fraction immobilized around the nanoparticles.
Several parameters influence the state of dispersion and exfoliation such
as the matrix type, the clay treatment and the processing conditions.
Polyamide 6 (PA6), also called Nylon 6, have been widely used in
packaging applications due to their good mechanical resistance, the high
barrier against gas and water, the fire resistance and the excellent
polyamide 6 induces an improvement in its properties and in particular
those related to barrier against water and gases.
In this work, the interfacial effects in polymer PA6/MMT nano­
composites were investigated by several techniques. Differential Scan­
ning Calorimetry (DSC) is such a technique, and it is used to study the
interfacial effects in polymer nanocomposites by focusing on glass
transition region. Indeed, Privalko et al. [3,4] recognized the impor­
tance of specific heat capacity measurements for the identification of a
fraction of reduced mobility in nanocomposites. Following these ideas,
the existence of a rigid amorphous fraction (RAF) in poly(methyl
methacrylate) (PMMA)/SiO2 nanocomposites was shown by applying
heat capacity measurements at the glass transition of the polymer as
described by Wunderlich et al. [5,6]. Then, a ‘3-phase-model’ was
established for semicrystalline polymers where the polymer matrix
consists of the mobile amorphous fraction (MAF), the crystalline fraction
(CF), and the RAF.
Complementary to thermal analysis, Broadband Dielectric spectros­
copy (BDS) is one of the most powerful methods used to evaluate the
different molecular mobilities of complex nanostructured systems and
provide an experimental access to the interfacial effects. The paper aims,
using the correlation between thermal and dielectric analysis, to

* Corresponding author.
E-mail address: imen.hammami1992@gmail.com (I. Hammami).

https://doi.org/10.1016/j.matchemphys.2019.04.048
Received 23 January 2019; Received in revised form 3 April 2019; Accepted 16 April 2019
Available online 20 April 2019
0254-0584/© 2019 Elsevier B.V. All rights reserved.
I. Hammami et al.
characterize the RAF induced by clay nanoparticles.
2. Experimental section
2.1. Materials
A commercially available polyamide 6 (Akulon, F132E1, DSM, NL)
with a molecular weight of 66000 g/mol and density of 1.13 g/cm3, was
used in this study. As reinforcement, the cloisite 30B (C30B) organo-
modified, contains the cation methyl tallow bis-2-hydroxyethyl, seems
to be a good choice. In fact, the cloisite 30B, as already shown before,
leads to a high exfoliation degree in PA6 [7]. The presence of hydrogen
bond between the hydroxyl groups and the amide groups of the polymer
chains facilitates the delamination.
2.2. Processing of PA6 nanocomposite films
The nanocomposites PA6/C30B were obtained using a two-step
treatment: the first step called masterbatch step, corresponded to the
preparation of a mixture containing the PA6 with 12% by weight of
C30B using a twin-screw extruder type Clextral BC45 at a rotation speed
of 50 rpm and a temperature ranging from 240 � C to 270 � C. The second
step was the dilution of this masterbatch into a Haake Buchler Rheocord
40 single-screw extruder at a temperature and screw speed of 230 � C and
50 rpm.
Nanocomposites films of 200–250 μm in thickness with different clay
content (3%, 5% and 7%) are finally obtained using single extrusion.
Prior to processing into films, the PA6 polymer and the nano-fillers
C30B are dried at 80 � C under vacuum overnight to remove residual
water moisture.
2.3. Experimental procedure
2.3.1. Transmission electron microscopy (TEM)
The morphologies of the nanocomposite films were analyzed by
transmission electron microscopy (TEM).
The specimens of 70 nm nominal thickness were cut with a diamond
knife on an ultracut microtome (Leica UCT, Switzerland), at cryo tem­
perature ( 120 � C).
Bright-field TEM images of nanocomposites were obtained at 300 kV
under low dose conditions with an electronic microscope (Philips
CM30), using a Gatan CCD camera (Gatan, USA).
2.3.2. Differential scanning calorimetry (DSC)
Differential Scanning Calorimetry (DSC) was performed to study the
effect of C30B incorporation on PA6 melting and crystallization
behavior, hence the percentage of RAF.
The DSC experiments were realized on a Mettler Toledo DSC-1 in­
strument under a nitrogen atmosphere at heating and cooling rate of
50 � C min-1 and 10 � C min-1 respectively. In all cases, the samples, with
a mass ranging between 2 and 4 mg, were heated from 90 � C to 250 � C,
cooled from 250 � C to 90 � C, then followed by a second heating step
from 90 � C to 250 � C.
The crystallinity index can be calculated from melting enthalpy by
the following relation:
XC ¼
ðΔHm ΔHc Þ
(1)
ΔHmo ð1 ϕÞ
where ΔHm is the melting enthalpy, ΔHc is the cold crystallization
enthalpy, ΔHm0 is the theoretical melting enthalpy of 100% crystalline
PA6 (ΔHm0 ¼ 190 J/g [8]) and ϕ is the mass fraction of C30B intro­
duced into PA6.
Temperature Modulated Differential Scanning Calorimetry (TMDSC)
is a method that allows a separation of reversing and non-reversing
processes. Hence, this technique provides more information about the
100
Materials Chemistry and Physics 232 (2019) 99–108
dynamics of the processes involved. In this study, stochastic TMDSC runs
were carried out on a Mettler-Toledo DSC1 instrument. The measure­
ments were made using samples with a mass of about 20 mg, at under­
lying heating rate of 1 � Cmin-1 between 60 � C and 250 � C. The
amplitude of the temperature pulse was set at � 0.5 � C and the switching
time range from 25 to 50 s.
2.3.3. Flash differential scanning calorimetry (Flash-DSC)
In order to evaluate the mobility of macromolecular chains in un­
filled films and composite films, Flash DSC experiments were performed
using a Flash DSC 1 instrument provided by Mettler-Toledo [9].
Contrary to conventional DSC instrument, a tiny fragment of sample
(with a mass in the order of nanograms) was placed onto a MultiSTAR
UFS 1 chip sensor, based on MEMS (Micro-Electro-Mechanical Systems)
sensor technology. Heating-cooling cycles in dry nitrogen gas are
essential to ensure that the sample has established a good thermal
contact to the sensor.
Measuring the weight of such low masses is not feasible with a
common balances. Therefore, the sample masses were estimated by
applying an identical protocol on the sample placed on the conventional
DSC and on another sample inserted in the Flash DSC. Finally, the
evaluation of the samples masses can be easily done via the melt
enthalpy determined from the two DSC curves. For the PA6 matrix, the
mass was estimated at 106 ng, while for the filled PA6, it was estimated
at 27 ng for PA6þ3%C30B, 131 ng for PA6þ5%C30B and 201 ng for
PA6þ7%C30B.
To study the kinetics of crystallization and nucleation, Flash DSC
measurements were made in a temperature range of 90 � C to 250 � C
using different heating and cooling rates (from 10 � Cs-1 to 1000 � Cs-1).
After carrying out the calorimetric measurements of the nano­
composite films, the RAF can be determined by applying the method
described by Xenopoulos and Wunderlich [10] for semi-crystalline
polymers. From the heat capacity measurements at the glass transition
region, they led to establish a model that makes it possible to distinguish
between the crystalline fraction CF, the rigid amorphous fraction RAF
and the mobile amorphous fraction MAF. This model is called a
three-phase model.
From the results obtained by the TMDSC and the DFSC, the RAF can
be determined using the following equation:
Xrað%Þ ¼ 1 ðXc þ xmaÞ (2)
where Xc is the crystallinity degree, calculated using eqn (1), and Xma is
the mobile amorphous phase fraction, deduced from eqn (3).
ΔCp
Xmað%Þ ¼ (3)
ΔCp ðamÞ
Δcp and Δcp(am) are the measured heat capacity increment at the
glass transition region of the semi-crystalline and 100% amorphous
polymer respectively. Δcp(am) can be determined experimentally by the
Flash DSC measurements or taken theoretically from ATHAS database
[11].
2.3.4. Dielectric Spectroscopy (DS)
Dielectric Spectroscopy measurements were performed on a Novo­
control Impedance Spectrometer based on an Alpha analyzer and a
Quatro temperature controller in the temperature ranged from to
20 � C–200 � C on heating at a rate of 5� Cmin-1 and in a broad frequency
window from 0.1 Hz to 1 MHz.
For the dielectric analysis, an alternating voltage with amplitude 1V
was applied to a sample placed between two parallel plate electrodes.
The measures dielectric permittivity data were collected and evaluated
using a WinDETA impedance analysis software.
The dielectric behavior is investigated with the complex dielectric
constant ε* and the complex electric modulus M * expressed as [12,13]:
I. Hammami et al. Materials Chemistry and Physics 232 (2019) 99–108

Fig. 1. TEM micrographs of (a, b) PA6 þ 3% C30B, (c, d) PA6 þ 5% C30B and (e, f) PA6 þ 7% C30B [14].

ε* ¼ ε’ jε} (4)

1 ε’
M* ¼ ¼ M’ þ iM} ¼ (5)
ε* ε’2 þ ε}2

where ε ’ is the real and ε ’’ is the imaginary parts of the dielectric

constant, M’ and M00 are, respectively, the real and imaginary parts of the
electric modulus.

3. Results and discussion

3.1. Morphological analysis

Fig. 1 shows TEM images of PA6 matrix and PA6/C30B nano­

composites taken at two magnifications (100 n.m. and 200 n.m.)
The TEM observation reveal that the PA6/C30B nanocomposites
contained individual nanoplatelets with more or less associated platelets
observed at law filler content. Therefore, PA6/C30B films present a high
degree of exfoliation of C30B nanoplatelets for the law and hight C30B
content. Moreover, the TEM images show a high degree of orientation of Fig. 2. DSC thermograms of PA6 matrix and PA6/C30B nanocomposites.
the nanoclay with an orientation parallel to the surface of the film. This
effect is associated to the processing condition, in other word to the presence of the nanoclay reinforcements. Therefore, it is necessary to
shearing forces induced in during the extrusion. These result are more determine the effect of the incorporation of these MMT nanolayers on
exploited in alix et al. research work [14]. the crystallinity degree. Fig. 2 shows thermograms obtained from ther­
mal analysis using differential scanning calorimetry (DSC). We note that
all the samples display an endothermic peak located in the region of
3.2. Crystalline structure and crystallinity
215 � C, associated with the fusion of the α-form crystals of PA6. We also
observe a second peak at 175 � C for the neat PA6 while it is centered at
In semi-crystalline polymers, the formation of the RAF can be
195 � C for the nanocomposites. This peak is due to the fusion of γ-form
affected by a change in the crystalline state of the material due to the

101
I. Hammami et al.
Table 1
Crystallinity index of PA6 matrix and PA6/C30B
nanocomposites.
Samples Xc (%)
PA6 27.7%
PA6þ3% C30B 30.9%
PA6þ5% C30B 31.8%
PA6þ7% C30B 31.4%
Fig. 3. Molar heat capacity of PA6 in the glass transition region: measured
curve for the semi-crystalline PA6;
amorph (Cp am) and cristal (Cp cr) reference curves from ATHAS
database; expected molar heat capacity from a 2-phase model; molar
heat capacity calculated from a 3-phase model; the tangent on the
measured curve above the glass transition region.
crystals. In fact, according to the literature [15–17], the PA6 exhibits a
polymorphic structure that presents two major crystal forms: the α-form
and the γ-form. This polymorphic behavior is dependent on the pro­
cessing conditions, thermal history, crystallization conditions and me­
chanical stress. The most thermodynamically stable phase is the α-form.
This phase has a monoclinic structure, in which the anti parallel polymer
chains are linked by hydrogen bonding. The γ-form crystal structure is
monoclinic or pseudo-hexagonal, in which hydrogen bonds are formed
between parallel polymer chains. Furthermore, the α and γ structures
coexist in the presence of MMTs in which the γ structure occurs near the
interfaces of the nanolayers. For the α structure, it develops where the
nanoplates do not affect the conformation of the chain and the folding of
the PA6. The cause of this is that MMT hampers the displacement of the
Hydrogen bonds associated with the transformation from γ structure to α
structure.
Therefore, the difference in melting temperatures of the γ-form
crystal between the pure PA6 and the nanocomposites may be due to a
growth in formation of crystal nuclei caused by the presence of MMT in
the nanocomposites.
From the two endothermic peaks associated with the fusion of the
α-form crystals and the fusion of the γ-form observed in the DSC ther­
mograms (Fig. 2) and using the equation (1), the crystallinity index Xc of
the samples could be deduced. These values are reported in Table 1.We
notice a slight increase in crystallinity index following the introduction
of MMT. This increase confirms the formation of new crystal nuclei
caused by the presence of MMT.
3.3. Determination of the rigid amorphous fraction
For semi-crystalline polymers, a RAF is broadly discussed [5]. This
fraction is defined as the polymer, which behaves liquid like, e.g.,
vitrified or devitrified in the common glass transition region (Tg) and
102
Materials Chemistry and Physics 232 (2019) 99–108
Fig. 4. Molar heat capacity of PA6 and PA6/C30B matrix in the glass transi­
tion region.
contributes therefore to the heat capacity step at Tg. According to the
DSC measurements, the RAF is considered completely rigid and does not
contribute to the glass transition. In order to determine the RAF, precise
measurements of heat capacity performed by the TMDSC technique in
the temperature range of the glass transition of the polymer nano­
composite are required.
Fig. 3 shows the evolution of the specific heat capacity of the PA6
determined by TMDSC (TOPEM) measurement.
The standard method evaluates the glass transition by using tangents
at the heat capacity curve above and below the glass transition region.
The glass transition temperature (Tg) is the temperature at which the
measured curve is equidistant between tangents. Then, the step height at
the glass transition Δcp is specified as the difference between the upper
and lower tangents at Tg.
In Fig. 3, the tangent below the glass transition coincides with the
heat capacity of the crystal (obtained from ATHAS database), while the
tangent traced above the glass transition is shown in dashed lines. In
order to fit the measured curve above Tg, a 2-phase model was applied
using the following equation:
Cpsc(2-phase model) ¼ Cpam � (1 CF)þCpcr � CF (6)
We note that the heat capacity measured just above the Tg is lower
than that expected from the 2-phase model. Consequently, a 3-phase
model, taking into account the RAF, has to be applied according to
Equation (7).
Cpsc(3-phase model) ¼ Cpam � MAF þ Cpcr � CF þ Cpra � RAF (7)
It is highlighted that for semi-crystalline polymers, two glass tran­
sitions can be detected. The first transition results from the MAF and the
second transition arises from the RAF [18].
Above the glass transition of the MAF, the RAF is still in the vitreous
state and it can be considered as solid and subsequently its heat capacity
is equal to the solid Cp.
Equation (7) can be described as follows:
Cpsc (3-phase model) ¼ Cpam � MAF þ Cpcr � SF (8)
Where SF ¼ CF þ RAF: solid fraction.
The comparison between the slope of the tangent traced above the
glass transition (dashed line) and the slope of the semi-crystalline heat
capacity shows a non-negligible contribution added to the measured
thermal capacity. This contribution can be either an excess heat ca­
pacity, or a continued extension of the glass transition to higher tem­
peratures (successive devitrification of the RAF) [19].
The same formalism can be applied for nanocomposites taking into
I. Hammami et al. Materials Chemistry and Physics 232 (2019) 99–108

Table 2 Table 3
The thermal parameters of PA6 and its nanocomposites: glass transition tem­ The thermal parameters of PA6 and its nanocomposites determined from Flash
perature (Tg), heat capacity step (ΔCp), crystalline fraction (CF), mobile DSC measurements at a heating rate of 1000 � C.s-1: glass transition temperature
amorphous fraction (MAF) and rigid amorphous fraction (RAF). (Tg), heat capacity step (ΔCp), crystalline fraction (CF), mobile amorphous
Sample Tg ΔCp (J CF (%) MAF RAF
fraction (MAF) and rigid amorphous fraction (RAF).
(� C) mol 1K 1) (%) (%) Sample Tg (� C) ΔCp (J CF MAF RAF
mol 1K 1) (%) (%) (%)
PA6 52 18.35 27.7 34.1 38.2
PA6þ3 wt% 51 15.63 30.9 29.1 40.0 PA6 60.5 36.93 21.8 68.7 9.5
C30B PA6þ3 wt% 61.5 32.7 28.1 60.8 11.1
PA6þ5 wt% 52 14.78 31.8 27.5 40.7 C30B
C30B PA6þ5 wt% 59.5 31.68 30.0 59.0 11.0
PA6þ7 wt% 53 14.07 31.4 26.2 42.4 C30B
C30B PA6þ7 wt% 60.5 28.14 33.6 52.4 14.0
C30B

Fig. 6. Diagram of time-temperature profile of the Flash DSC experiments used

to investigate the nucleation and crystallization in PA6 and PA6/C30B films.

Fig. 5. Flash DSC thermograms of PA6 matrix and PA6/C30B nanocomposites.
account the crystalline fraction from MMT incorporation [20]. To
determine the RAF, the heat capacity measurements, using the TOPEM
method, in the temperature range of the glass transition were performed
for the different samples of PA6/C30B. The results are shown in Fig. 4.
As shown in Fig. 4, the heat capacity curves are shifted towards lower
values by increasing filler concentration. The lowering is due to a part of
the polymer immobilized by the C30B which does not contribute to the
glass transition.
From the obtained curves, the heat capacity step at Tg of PA6 and its
nanocomposites can be determined. Eventually, the MAF and the RAF
can be deducted. The value of ΔCp(am) used for the calculation of the
MAF is determined from the ATHAS database. This value corresponds to
53.7 J.K-1.mol. The ΔCp, MAF, CF and MAF are available and given in
Table 2. From the Table 2, it can be noticed that ΔCp is directly related
to MAF. This result means that MAF decreases in the presence of MMT.
Therefore, the increase in the percentage of MMT introduced in the PA6
causes the increase of the RAF. The incorporation of the nanoparticles in
the matrix affects the polymer layer adjacent to these additives by
stopping the movement of this layer. Consequently, this reduction in
molecular mobility tends to increase RAF. In addition, the RAF is related
to the degree of dispersion of C30B in the matrix [21]. In fact, the per­
centage of RAF increases for nanocomposites with a higher degree of
dispersion and higher clay content. This is the case of PA6þ7 wt% C30B
nanocomposite which is exfoliated and has the higest clay content [7]. It
can be expected that the RAF will increase with increasing the filler
content. However, at a high filler content, it is known that the C30B
tended to aggregate and that will lead to the decrease of the RAF [22,
23].
To confirm the results obtained by the TMDSC technique, the Flash
DSC was used in this study. To calculate the RAF, the same approach
described previously was used. The results were calculated and shown in
Table 3. The values of ΔCp and ΔHf are determined from the Flash DSC
curves (Fig. 5). Subsequently, a correction of these values with respect to
the masses of the samples was made.
The results observed in Table 3 confirm that obtained from the
TMDSC measurements despite the remarkable difference in the per­
centages of MAF and RAF. This difference is due to the fact that in these
two techniques we did not use the same heating and cooling rates.
3.4. Nucleation and crystallization kinetics
As known, Flash DSC is the ideal technique for studying nucleation
and crystallization kinetics in PA6 and PA6/C30B nanocomposites
during cooling. A simple analysis protocol is schematized in Fig. 6.
The advantage of this analysis is its ability to acquire additional in­
formation on the crystallization, nucleation and stability of objects
formed by controlled cooling. In fact, information on the interaction of
the growing objects and the surrounding melt can be determined from
changes in the increase in thermal capacity at Tg. Then, the available
mobile and crystallizable material is given by the analysis of the cold
crystallization peak. In addition, in noncrystalline samples, the cold
crystallization enthalpy appears to be a good measure of the number of
available nuclei, and the temperature of the cold crystallization range is
related to changes in the type of nuclei present. Finally, the melting
temperature of the different species can be related to the stability of the
objects and the change of total enthalpy at heating provides information
the total crystallinity present in the sample before the heating scan [24].
A set of heating curves after cooling at different rates is shown in
Fig. 7.
For PA6, the melting peak decreases and becomes zero at cooling
rates above 500 � C.s-1. Then, no crystallization occurs in this case.
At low cooling rates, the nanocomposites show at the glass transition
range a relatively small and broadened increment, no cold crystalliza­
tion and a large melting peak. While for higher cooling rates, the
increment in the glass transition increases and becomes more noticeable

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I. Hammami et al. Materials Chemistry and Physics 232 (2019) 99–108

Fig. 8. Temperature dependence of real (a) and imaginary (b) parts of the
dielectric permittivity for the PA6 matrix.

Fig. 7. Apparent heat capacity of: (a) PA6, b) PA6þ3%C30B, c) PA6þ5%C30B,
d) PA6þ7%C30Bfrom Flash DSC on heating with 1000 � C/s after cooling with
rates between 50 and 1000 � C/s.
due to the onset of a cold crystallization peak. This peak develops and its
intensity increases for high cooling rates. This increase is explained by a
growth in the formation of crystalline nuclei. In addition, the melting
peak decreases as a result of low crystallinity developed during cooling.
It can be deduced that, depending on the cooling rates, different
states of the materials can be detected allowing modeling of their
thermal histories. Indeed, a slow cooling leads to a thickening and better
stability of the crystallites. This thickening occurred through homoge­
neous and heterogeneous nucleation followed by growth, i.e., the
transformation of low-perfection crystallites into thicker crystalline
lamellae with a higher degree of perfection. By increasing the cooling
rate, the sample cannot complete its crystallization during cooling.
Initially, a homogeneous and heterogeneous nucleation occurs but fewer
crystals grow. The remaining nuclei induce cold crystallization.at higher
rates of cooling the homogeneous and heterogeneous nuclei in their
growth do not reach a perfect size, i.e., the amount of crystals continues
to decrease, which causes the decrease of the melting peak. On the other
hand, the amount of nuclei continues to increase causing the increase of
the peak of cold crystallization.
Furthermore, the Fig. 7 can provide information regarding the
enthalpy relaxation of the polymer, which is also characteristic of a
physical aging. It is known that the rate at which you cool through Tg
has a considerable effect on the resulting ageing kinetics [25,26]. A
slower cooling rate gives more time for the molecular chains to find
energetically favorable orientations. For the PA6, it can be observed a
peak of enthalpic relaxation at the glass transition region, which is more
remarkable for the slowest cooling rate. In factthe PA6 has the time to

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I. Hammami et al. Materials Chemistry and Physics 232 (2019) 99–108

Fig. 10. The dielectric loss data ε" and the corresponding derivative data
ε00 deriv at 150 � C for the PA6 matrix.

Fig. 9. Frequency dependence of imaginary of the dielectric permittivity (a)

and imaginary (b) for the PA6 matrix.

undergo a physical aging at and below the Tg. The shorter the time (fast
speed) the less physical aging.
For the nanocomposites this phenomenon is less observable when the
C30B content introduced in PA6 increases until disappearing at 7% of
C30B content. This could be related to the increase of RAF with
increasing the filler content. Indeed, the presence the RAF will affect the
behavior of the mobile amorphous phase. Consequently, the phenome­
non of enthalpy relaxation decreases with the increase of the rigid
amorphous phase [27,28].

3.5. Dielectric study

Fig. 8 depicts the temperature dependence of the dielectric permit­

tivity ε0 and the loss factor ε00 , respectively, for the PA6 matrix. As it can
be seen, three relaxations are observed:

- The primary relaxation, α-relaxation, appears for temperatures be­

tween 40 and 140 � C and frequencies between 102 and 106 Hz. It is
associated to the glass transition of PA6 matrix [29–31].
- The αc-relaxation occurs between 60 and 200 � C (between 10–1 and
104 Hz). According to Laredo et al. [32], in the case of PA6, this kind
of relaxation may be related to the presence of crystalline phases or
to the diffusion of carriers such as protons and other impurities.
- The ionic conduction process observed at high temperature and a
low-frequency ranges, which appears from the increase in the elec­
tric charges mobility in the polymer with temperature, resulting a
Fig. 11. Imaginary part of the dielectric modulus M00 versus frequency, at 70 � C
(a) and at 150 � C (b), for the PA6 matrix and PA6/C30B nanocomposites.
large increase in both the real and imaginary parts of the dielectric
function [33].
In the same way, the variations of the loss factor ε ’’ can be presented,
in isothermal conditions (Fig. 9a). These variations show a linear in­
crease of ε ’’ especially for the high temperatures and the low

105
I. Hammami et al.
Fig. 12. Imaginary part of the electric modulus M00 versus frequency for the
PA6þ7%C30B nanocomposites. at 70 � C (a) and at 150 � C (b).
frequencies. In these domains the slope of ε ’’ is close to 1, which in­
dicates the presence of DC conductivity effect [34,35].
This phenomenon can be detected by presenting the frequency
dependence of the AC conductivity. As it can be seen from Fig. 9.b, the
presence of a horizontal plateau at low frequencies corresponds to the
DC conductivity effect. Moreover, we notice a slight decrease of AC
conductivity at low frequencies. This behavior is related to the elec­
trodes polarization mechanism [36,37].
To further investigate the phenomena that occur at low frequencies
region, we use the first derivative of the real part of the dielectric
permittivity [38]:
π ∂ε’
ε’’deriv ¼
2 ∂lnω
The ε’’deriv method is useful for systems that exhibit low frequency
relaxations with appreciable ohmic conductivity, since the values of ε
0
(ω) are unaffected by ohmic conductivity, and according to Kramers-
Kroning relationships its derivative is proportional to the loss factor ε
’’ (ω). Indeed, in the derivative formalism, the relaxation processes that
take place in the dielectric loss variations appear as sharper peaks and
without contribution of conductivity [39].
In the Fig. 10, we compare the dielectric loss data ε’’ , ε’’deriv at 150 � C.
From the variations of ε’’deriv , and as it can be seen, we note the presence
of three relaxation phenomena: relaxation αc, interfacial polarization
MWS that appears due to the differences in conductivity values of the
crystalline and amorphous phases and the electrodes polarization PE.
The frequency dependence of M00 for PA6 and the nanocomposites at
two different temperatures is display in Fig. 11. At low temperature
(70 � C) the α relaxation is observed for the four samples (Fig. 11a). The
Materials Chemistry and Physics 232 (2019) 99–108
Fig. 13. Relaxation map corresponding to the temperature dependence of the
relaxation time for α, αcand MWS processes for PA6 matrix and PA6/C30B
nanocomposites.
αc relaxation and interfacial polarization appear in the frequency win­
dows at higher temperatures (Fig. 11b at 150 � C).
The effect of clay-nanoparticles on the segmental mobility is further
analyzed by performing an analysis based on fitting appropriate model
functions. The electric modulus spectra were fitted by a sum of
Havriliak-Negami (HN) model function terms of the form. The equation
is an approximation of the HN equation [40]:
2 3
X n
6 Msi M∞i 7
*
M ðωÞ ¼ 4M∞i þ h �αi iβi 5 (10)
1
i¼1 1 þ ð jðωτi Þ
where ω ¼ 2π f the angular pulsation, τ the relaxation time and α and β
the symmetric and asymmetric broadening factor.
To better distinguish the different mechanisms observed, a separa­
tion of overlapping relaxation regions via the deconvolution of the
imaginary part of the electric modulus M00 is presented in the Fig. 12.
We note a good agreement between the experimental data and the
obtained modelizations.
From the data obtained by the adjustment, the maximum relaxation
times versus the reciprocal of the temperature can be traced as can be
seen in Fig. 13.
The temperature dependence of the relaxation rate for the MWS-
relaxations were described by the Arrhenius equation [41]:
�
Ea
�
τ ¼ τ0 exp (11)
kB T
(9)
where Ea is the activation energy, τ 0 the pre-exponential time,
kB ¼ 1.38 � 10–23 J K-1 is the Boltzmann constant and T the absolute
temperature.
The α and αc relaxations were better described by a VFT
(Vogel–Fulcher–Tammann) equation [42–44]:
� �
τðTÞ ¼ τ0 exp
DT0
(12)
T T0
where τ0 is a pre-exponential factor, T0 is Vogel temperature (ideal glass
transition), it was found to lie between 30 and 70 K below glass transi­
tion temperature Tg [37]. D, the so-called strength parameter [45], is a
measure of the fragility factor describing a deviation of the temperature
dependence of τ (T) from the Arrhenius behavior.
The curves in Fig. 11 showed that the relaxation time decreases with
increasing temperature. In addition, one can note that each relaxation
process manifests itself in the same temperature range for the different
106
I. Hammami et al.
Table 4
Calculated activation energies EA and strength parameter D.
Samples EA (eV) D effect on oligo-ethylene glycol adipate (oega) properties, Polym. Sci. 12 (1970)
α-Relaxation PA6 – 3.85
PA6-3%C30B – 5.56
PA6-5%C30B – 5.64
PA6-7%C30B – 5.76
αc-Relaxation PA6 – 10.05
PA6-3%C30B – 10.51
PA6-5%C30B – 12.61
PA6-7%C30B – 14.32
Interfacial polarization MWS PA6-7%C30B 1.209 – and optical properties of polyamide 6/clay nanocomposite cast films: influence of
samples, except the interfacial polarization which appears in the same
temperature range of αc relaxation. This may reveal a similarity of these
two processes, i.e., αc can be considered as an interfacial polarization.
This result is in good agreement with those found by Laredo et al. [32]
who considered that the relaxation αc is related to the interfaces be­
tween the amorphous and crystalline regions. The resulting parameters
for the observed relaxation processes are listed in Table 4. We find that
the values of the fragility parameters D for the relaxation α and αc in­
crease considerably as a function of the reinforcement rate indicating
the reinforcing effect of the clays, which limits the mobility of the PA6
chains. The interfacial polarization can be assigned to the interfaces
between the filler and the polymer. This can be confirmed by the
quasi-inexistence of this relaxation for the PA6 matrix and the nano­
composite with low filler content. This relaxation intensity increases
with the filler content.
For the PA6-7%C30B nanocomposite, the activation energy is very
high and comparable to that found by other authors [46]. This important
value reflects the strong interactions between clay nanoparticles and
PA6 matrix.
4. Conclusions
In summary, thermal and dielectric properties of PA6/MMT nano­
composites were investigated. DSC analyzes allowed to highlight the
existence of an immobilized fraction through measurements of the
thermal capacity during the glass transition. At higher C30B content
incorporated in the PA6 matrix, this fraction becomes larger. This means
that two different parts of the RAF must be considered by analyzing the
heat capacity of the semi-crystalline nanocomposites, one immobilized
at the interface between the crystallites and the amorphous polymer and
the other at the interface between the filler and the polymer.
In addition, the Flash DSC analyzes provide new quantitative
knowledge on the kinetics of crystallization and nucleation of PA6 and
its nanocomposites. We have noticed that crystallization at high cooling
rates may be related to an increase in nucleation density; while for low
cooling rates the crystal growth rate is faster than the nucleation rate.
Concerning the dielectric study, different relaxation processes have
been detected for PA6 matrix and nanocomposites. These processes were
mainly associated to the relaxation α associated with the glass transition
of the amorphous mobile phase of polyamide 6 and the relaxation αc
related to the interfaces created between the amorphous phase and the
crystalline phase. Moreover, the incorporation of MMT into PA6 matrix
gave rise to another relaxation associated to MWS interfacial polariza­
tion. This latter arises from the trapping of electric charges at the in­
terfaces between the MMT nanoparticles and the PA6 matrix. This later
is well defined for the nanocomposite with 7% reinforcement. Thus, lead
to the same results obtained by the TMDSC analysis.
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