Polymer 120 (2017) 255e263

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Self-organized microporous cellulose-nylon membranes

Evie L. Papadopoulou a, *, 1, Jose

Alejandro Heredia-Guerrero a, **, 1, Maria Isabel Va

zquez b,
b a a
Juana Benavente , Athanassia Athanassiou , Ilker S. Bayer
a
Smart Materials, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genoa, Italy
b
Departamento de Física Aplicada I, Grupo de Caracterizacio
n Electrocin

etica y de Transporte en Membranas e Interfases, Facultad de Ciencias, Universidad

laga, E-29071 Ma
de Ma
laga, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Microcrystalline cellulose (MCC) and polyamide 66 (PA66) have been separately dissolved in solutions
Received 12 April 2017 containing trifluoroacetic acid (TFA) as a common solvent, mixed after their dissolution and cast. After
Received in revised form solvent evaporation, self-organized membranes have been formed with three dimensional (3D) porous,
1 June 2017
interconnected morphology, the porosity of which depends on the relative ratio of cellulose and PA66,
Accepted 2 June 2017
Available online 5 June 2017
and is lost when the initial MCC content exceeds 50% by weight. Thermal and chemical analysis and X-
ray diffraction results indicate that the addition of cellulose induces the amorphisation of PA66, while
possible chemical interaction exists between the amorphous parts of PA66 and the cellulose. The various
Keywords:
Polyamides 66
membranes produced with different 3D porosities have been characterized in terms of dielectric con-
Microcrystalline cellulose stant and salt permeability and their relation to cellulose-PA66 ratio has been determined.
TFA © 2017 Elsevier Ltd. All rights reserved.
Composites
Porosity
Membranes

1. Introduction processes, could be time consuming and expensive. Recently, a

Three dimensional (3D) porous materials of various composi-
tions like bones, wood, or mycelia are common building blocks of
most of the living organisms, and provide a source of increasing
inspiration in materials engineering. In addition, the use of natural
or synthetic polymeric materials and especially their composites,
provides a wide range of possibilities to manipulate and finally
tailor their physical properties, offering materials with various
functionalities [1]. It is, thus, accepted that biomimicry offers
meaningful solutions in fabricating porous, 3D structures of poly-
meric composites that are used in a wide range of applications,
spanning from tissue engineering [2], to water purification [3] or
sensor applications [4].
The fabrication methods for porous, 3D polymeric structures
include solvent inversion [5], phase separation [6], gas foaming [7],
rapid prototyping [8], use of supercritical CO2 [9], etc. These
methods often require specific equipment or post-fabrication
* Corresponding author.
** Corresponding author.
E-mail addresses: paraskevi.papadopoulou@iit.it (E.L. Papadopoulou), Jose.
Heredia-Guerrero@iit.it (J.A. Heredia-Guerrero).
1
Authors have contributed equally to the research presented in the article.
more approachable method is being explored, namely the self-
assembly [10], defined as the spontaneous method of organiza-
tion of various components into structures, without external
intervention. It has been used to fabricate porous, PCL-based
membrane films [11,12], polyethylene membranes [13] or cellu-
lose nanocrystals [14].
Microporous polymer networks constructed from polymer
blends constitute a relatively new state-of-the-art in materials
engineering [15,16]. Combining polymers with dissimilar proper-
ties, such as hydrophobicity/hydrophilicity, rigidity/softness,
chemical inertness/controlled solubility, to form 3D porous struc-
tures, offer many advantages over single polymer systems, such as
enhancement in affinity or repellency towards a specific liquid
(wetting properties), gas adsorption, or ionic conductivity (power
devices). In the present work, we have used a simple solution
processing method, with consequent self-assembly during evapo-
ration, similar to the one presented in Ref. [12], to fabricate porous
films with tuned 3D interconnectivity, from cellulose (MCC) and
polyamide (PA66). The technological importance of both materials
is enormous, since cellulose is the most abundant natural polymer,
widely used in biodegradable polymer structures [17,18] and
membrane applications [19], while polyamides are synthetic ther-
moplastic polymers extensively used in many technological

http://dx.doi.org/10.1016/j.polymer.2017.06.002
0032-3861/© 2017 Elsevier Ltd. All rights reserved.
256 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263
applications [20e22]. For the solution processing, TFA is used as a
common solvent. The solution cast films exhibit a porous, 3D
interconnected structure, the porosity of which depends on the
relative ratio of the two components. Solution processing of cel-
lulose and polyamide composites is difficult because it is difficult to
find a common solvent for both materials. To the best of our
knowledge, only Garcia-Ramirez [23,24] used a solution process in
order to dissolve cellulose and PA66, to fabricate composite fibres
or films of PA66 and study their chemical and mechanical proper-
ties, using a mixture of N-methylmorpholine N-oxide (NMMO) and
phenol. Recently, however, it was shown that trifluoroacetic acid
(TFA) is a common solvent for both MCC [25,26] and PA66 [27].
Chemical analysis of the porous films indicates that at least part
of the PA66 is homogeneously mixed with the cellulose. The me-
chanical properties of the blends are not found to deviate from the
mechanical properties of pure PA66 or cellulose films prepared
with the same method. Finally, the porous structures are charac-
terized by impedance spectroscopy and salt permeation and
compared with existing membranes. Impedance spectroscopy is a
widely used technique to study the electrical properties of poly-
meric membranes. It is particularly used to assess the behaviour of
synthetic membranes during separation processes and carry out
fundamental studies on membrane-based sensors [28]. Further-
more, permeability of salts (Ps) through polymer membranes is an
important phenomenon studied for desalination processes. It
strongly depends on the polymer structure (i.e. the presence of
pores and free volume elements in the polymer matrix) and the
hydrophilicity of the membrane [29]. It is found that both transport
and permeation properties are tuned by the concentration of cel-
lulose in the composite, and that our composite cellulose-PA66
films can potentially be used as membranes for controlled salt
diffusion, with tunable surface morphology and porosity.
2. Experimental
2.1. Materials
Microcrystalline cellulose powder (MCC), polyamide 6.6 (PA66),
trifluoroacetic acid (TFA) and acetone were purchased from Sigma-
Aldrich. All the chemicals were analytical grade and used as
received, without any further purification. Regenerated cellulose
(0.04 kg/m2) was purchased from Cellophane Espan ~ ola, S.A. (Spain).
Porous Nylon 66 (PA66) membrane was purchased from Sartorious
AG (Germany).
2.2. Sample preparation
MCC was dissolved in TFA (3% w/v) and PA66 was dissolved
separately in 1:1 mixture of TFA:acetone (7% w/v). The dissolution
of the materials took place in ambience, for 48 h for the MCC and
24 h for the PA66. Subsequently, the two polymer solutions were
mixed at appropriate volume ratios, resulting in clear and homo-
geneous solutions, for all cellulose/PA66 ratios, from 100:0 to 0:100.
The mixtures were cast into plastic petri dishes, covered and left to
dry slowly at ambient conditions, and thus free standing films were
obtained. The films were left under the hood for at least one week,
in order to ensure that all TFA was released, prior to any experi-
ment. Following these evaporation conditions resulted in repro-
ducible structures for all cellulose-PA66 ratios. The samples were
named according to both concentrations. For example, M50P50
means the sample contains 50% MCC and 50% PA66 by weight.
2.3. Sample characterization
2.3.1. Morphological characterization and porosity
The surface and cross-section morphology of the films were
studied by scanning electron microscopy (SEM, JEOL JSM-6490LA),
with an acceleration voltage of 10 kV.
The porosity (or void fraction) of the membranes was calculated
as follows. A round disc (diameter of 1 cm) of specific volume is cut
out of the films, it is weighed and its density, dpristine, is calculated.
Subsequently, the disc is pressed (10 tons, 10 min) in order to
remove all the air from the membrane and its density, dpressed, is
calculated again. Then, the relative density is calculated by
Ref. [30]:
dpristine
drelative ¼ (1)
dpressed
and the porosity, or volume fraction, Vf, is given by:
Vf ¼ 1  drelative (2)
2.3.2. Thermal characterization
Thermal studies were carried out using thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC). The
degradation temperature of the materials was evaluated by TGA.
During TGA measurements, samples were heated from 30  C to
600  C at a heating rate of 10  C/min under nitrogen atmosphere set
at a flow rate of 50 ml/min. Differential scanning calorimetry (DSC)
was performed using a Q-20 TA-Instruments, calibrated with an
indium standard, at a heating rate of 20  C/min. Dry samples
weighing ca. 10 mg were placed in aluminum pans and tested
under an inert N2 atmosphere. The samples were first heated
from 60  C to 110  C, kept at this temperature for 10 min and
cooled back to 60  C. Subsequently, during the second scan the
samples were heated to 271  C (above the melting point of PA66),
cooled to 60  C, followed by a final third scan to 300  C. The
calorimetric melting temperature (Tm) and the enthalpy of fusion
(DHm) of each sample were calculated from the maximum and the
area of the melting peak of the third scan, respectively.
2.3.3. Crystallinity and chemical structure
The crystal structure was studied by X-ray diffraction (XRD)
using a Rigaku SmartLab X-Ray diffractometer, equipped with a
9 kW Cu Ka (l ¼ 1.542 Å) rotating anode, operating at 40 kV and
150 mA. A Go € bel mirror was used to convert the divergent X-ray
beam into a parallel beam and to suppress the Cu Kb radiation
(l ¼ 1.392 Å). The diffraction patterns were collected at room
temperature, over an angular range of 5 e40 , with a step size of
0.05 and scan speed of 1.2 /min.
Infrared spectra were obtained with Fourier Transform Infrared
Spectrometer (FTIR; Equinox 70 FT-IR, Bruker) equipped with an
attenuated total reflectance accessory (ATR; MIRacle ATR, PIKE
Technologies). All spectra were recorded in the range from 4000 to
600 cm1 with a resolution of 4 cm1, accumulating 128 scans. For
the evaluation of the shift for Amide I and II bands, three spectra
per sample were collected in the range 1700 to 1500 cm1, with a
resolution of 1 cm1, accumulating 128 scans.
2.3.4. Mechanical properties
Mechanical properties were investigated by tensile stress
measurements using an dual column tabletop universal testing
 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263
System 3365 with 5 mm/min cross-head speed. The Young's
modulus, maximum stress and elongation at break were calculated
for each sample and average values are reported. The tensile
measurements were conducted on five different specimens for
each film according to ASTM D 882 Standard Test Methods for
Tensile Properties of Thin Plastic Sheeting.
2.3.5. Water uptake
Water uptake, Wu, was measured by immersing a small piece of
the films into nanopure water and weigh it repeatedly, until no
change in the weight was measured. The water absorption is then
calculated by:
Wwet  Wdry
Wu ¼  100
Wdry
where Wwet and Wdry are the weight of the dry sample and the
wetted one, respectively.
2.3.6. Impedance spectroscopy measurements
The cell used for impedance spectroscopy (IS) measurements
consists of a Teflon support on which two Pt electrodes are placed,
forming a Pt-electrode/membrane/Pt-electrode system. The elec-
trodes are connected to a Frequency Response Analyzer (FRA,
Solartron 1260, UK). The measurements were recorded for 80 data
points for frequency (f) ranging between 100 Hz and 107 Hz, at a
maximum voltage of 0.01 V, in ambience (23  C, 55% RH).
The impedance of a system is a complex number,
Z ¼ Zreal þ jZimg , where Zreal and Zimg are the real and imaginary
parts of the impedance, Z, respectively. For simple systems (one
time constant), Zreal and Zimg are related to the electrical resistance
(R) and the capacitance (C) by the following expressions:
R uR2 C
Zreal ¼ h i and Zimg ¼ h i (4)
1 þ ðuRCÞ2 1 þ ðuRCÞ2
Fig. 1. SEM images of the surface of (a) M25P75, (b) M50P50, (c) M75P25 are shown. In (d) the cross section of M50P50 is shown.
257
where u is the angular frequency (u ¼ 2pf). In the case of non-
homogeneous systems, a non-ideal capacitor or constant phase
element, Q ðuÞ ¼ Y0 ðjuÞn is considered instead of C [31,32], where
Y0 is the inverse of the impedance (Y0 ¼ 1/Z) and n is an experi-
mental parameter (0  n  1).
2.3.7. Salt diffusion measurements
NaCl diffusion measurements were performed in dead-end test
cells, similar to that described in Ref. [33]. The membrane is placed
in the middle of two symmetric half-cells, separating a feed solu-
tion (Cf ¼ 0.01 M) from a receiving solution (Cr, initially distilled
water), which are stirred at a rate of 540 rpm by two magnetic
stirrers in order to minimize concentration-polarization at the
(3) membrane/solution interface. Time variation of feed and receiving
solutions conductivities are recorded with two conductivity cells
connected to a digital conductivity meter (Crison GLP 31), each one
placed in each half-cell. Measurements were carried out at room
temperature and solutions standard pH (5.8 ± 0.3). A calibration
curve (NaCl solution conductivity versus concentration) was used
to determine the solution concentration. The calculation of the salt
permeability is shown in the SI.
3. Results and discussion
3.1. Morphology of the composite films
The SEM images of the different polymer blends are shown in
Fig. 1. While pure cellulose presents a flat surface (as shown in
Ref. [25]) and pure PA66 a rough, dense surface morphology (SEM
image of PA66 films, at SI), the surface morphology of the blends is
different. In Fig. 1(a) and (b) the blends with 25 wt% and 50 wt%
cellulose, respectively, display 3D structures with different poros-
ities. The porosity is calculated using Equations (1) and (2) and is
22% for M50P50 and 8% for M25P75. For higher cellulose content,
the porosity is lost, as seen in Fig. 1(c), where a rough surface is
present, without, however, porous structure. In Fig. 1(d), the
membrane formation is confirmed by cross-section SEM images,
258 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263

where it is seen that the porous structure is present throughout the
bulk of the M50P50 film.
3.2. Chemical analysis
FTIR measurements were performed in order to chemically
characterize the blends, as depicted in Fig. 2(a). Pure cellulose and
pure PA66 films show the respective typical absorption bands of
cellulose (OH stretching at 3354 cm1, CH stretching at 2889 cm1,
adsorbed water at 1643 cm1, ring breathing at 1155 cm1, and CeO
stretching at 1016 cm1) [25] and PA66 (amide A at 3296 cm1,
amide B at 3082 cm1, asymmetric and symmetric CH2 stretching at
2934 cm1 and 2860 cm1, respectively, amide I at 1632 cm1,
amide II at 1537 cm1, amide III at 1198 cm1 and amide V at
689 cm1) [34]. Characteristic infrared vibrations of the solvents
are not observed, indicating no residual polymer bound surface.
Absorption spectra of the blends are characterized by the presence
of both cellulose and PA66. Interestingly, as the cellulose concen-
tration increases, both amides I and II shift to higher wavenumbers
(blueshift), as depicted in Fig. 2(b) and (c). Amide I is conforma-
tional sensitive [35], meaning that conformational differences,
caused by the addition of another material like cellulose, between
different nylon structures will result in a shift of the amide I peak.
Furthermore, the blue shift of amide I is also associated to the
weakening of the H-bond to the carbonyl group [36e38]. The
weakening of the H-bond will manifest itself as a blueshift, because
the frequency of the amide I is related to vibrations of the H-bonded
C]O from both the amorphous and the crystalline phases of PA66.
As it has been shown by Lu et al. [38], the vibrational frequency of
the amide I in PA66, is lower for the crystalline domains, and higher
for the amorphous domains. It is thus understood that shifting of
the amide I to higher frequencies (blueshift) indicates an increase of
the amorphous phase and the consequent weakening of the H-
bonds. This leads to the assumption that the addition of cellulose in
the blend, results in the amorphisation of PA66, as will be shown in
a later section.
In the present case, it is also possible that PA66 and cellulose
interact via the hydroxyl groups of the polysaccharide and the
amine and carbonyl groups of the polyamide, as shown in Fig. 2(c).
3.3. Thermal and structural characterization
The thermal degradation of the blends characterized by TGA is
shown in Fig. 3(a). The degradation temperature of PA66 starts at
ca. 360  C (~2 wt% material remaining at 600  C), while the
degradation of cellulose starts at a lower temperature, ca. 280  C
(~20 wt% material remaining at 600  C). The curves of the blends
fall between these two extremes and the remaining material at
600  C increases with the increasing content of cellulose in the
blends. In Fig. 3(b), the temperature of the maximum degradation
of the PA66 and cellulose, taken from the derivatives of the ther-
mographs (shown in SI), is plotted as a function of cellulose con-
centration. It is seen that the peak position of PA66 moves ca. 13 to
higher temperature with increasing cellulose content, whereas the
peak position of cellulose moves ca. 14 to lower temperature, with
increasing cellulose content. The shift of the PA66 degradation
temperature to higher temperatures can be explained by the
presence of new bonds that result in increased thermal stability.
This interaction should take place via H-bonds, between PA66 and
cellulose, and is expected to disrupt the crystalline order of PA66,
and lead to its amorphisation.
This finding is further supported by DSC studies. The DSC
thermographs of pure PA66 and PA66/cellulose blends are depicted
in Fig. 4(a). The endothermic peaks observed correspond to the

Fig. 2. (a)ATR-FTIR spectra of cellulose, nylon and their corresponding blends. Main assignations of cellulose and nylon peaks are shown. (b) Amide I and amide II vibrations of PA66
and blends. (c) The blueshift of amide I (black) and amide II (red) vibrations as a function of cellulose concentration. The insets represent different secondary interactions by H-
bonds for nylon, cellulose and their blends. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263 259

Fig. 3. (a) TGA thermographs for PA66, cellulose films and their corresponding blends. (b) The position of the cellulose and PA66 peaks with respect to cellulose concentration of the
blends.

Fig. 4. (a) DSC thermograms of PA66/cellulose blends. (b) Variation of melting temperature (black circles), and the enthalpy of fusion (red, open circles) with the content of
cellulose. (c) Variation of the thickness of nylon crystallites with the content of cellulose. The insets show two models at molecular level of samples of pure nylon (left) and high
cellulose content (right). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

melt of the PA66. As expected, the PA66 films formed after the
dissolution of PA66 and solvent evaporation, show two melting
peaks at approximately 250  C (Tm1) and 260  C (Tm2), attributed to
less crystalline and more crystalline lamellae, respectively, formed
during re-crystallization [27]. As shown in Fig. 4(b), the increase of
cellulose concentration (with the concomitant decrease of PA66
concentration in the blend), results in a shift of Tm2 to lower tem-
peratures. Furthermore, the heat of fusion, DHm, which equals the
area under the peak and is directly proportional to the degree of
crystallinity, is estimated from the DSC curves and is also shown in
Fig. 4(b). Both the depression of melting point and the amorph-
isation of nylon can be explained by a decreasing size of nylon
crystallites and/or an increasing dissolution of cellulose in nylon
[39,40]. In order to account for the different PA66 concentrations,
the calculated heat of fusion is normalized for the PA66 concen-
tration by DHm norm¼(DHm/PA66 wt%)  100. The DHm is seen to
decrease with increasing cellulose concentration. Both the shift of
Tm2 to lower temperatures and the decrease of DHm with increasing
cellulose concentration indicate an amorphisation of PA66.
The amorphisation of PA66 in the blend, with increasing cellu-
lose content, is expected to lead to the size reduction of the PA66
crystallites. Hence, the crystallite size has been calculated using the
Thompson equation:
 
2s
Tm ¼ Tmo 1  (5)
rDHm l
where Tm and Tmo are the melting temperatures of the sample and
the perfect crystals (301  C), respectively, s is the interfacial energy
of crystallites (69  103 J/m2), DHm and r are the heat of fusion
(190 J/g) and the density (1.22  106 g/m3), respectively, of crys-
talline PA66 and l is the thickness of crystallites [23]. In Fig. 4(c) it is
seen that the size of the PA66 crystallites decreases, though not
significantly, with cellulose concentration, except for M75P25.
Similar results have been observed also by Garcia-Ramirez [23]
in cellulose-PA66 composites, in which PA66 domains are well
260 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263
Fig. 5. (a) XRD diffractograms of the PA66 and cellulose films, and their blends. (b) The d spacing for (100) and (010) planes, as a function of the cellulose content.
dispersed in the cellulose matrix. The small variation of PA66
crystallites, for low cellulose content, indicates that the amorphous
part of PA66 does not depend on the cellulose content. The
exception is sample M75P25, where the thickness of the PA66
crystallite is almost half, indicating the expansion of the amorphous
PA66 at high concentrations of cellulose.
In Fig. 5(a) the X-ray diffractograms are shown for the different
blends. PA66 exhibits two peaks at approximately 20 and
24 corresponding to (100) and (010)/(110) doublet, respectively,
while cellulose has the characteristic pattern for the cellulose II
polymorph, as expected for the solvent used for the preparation of
the films [27,41,42]. Strong and sharp reflection peaks indicate
crystalline, well-ordered structures, whereas weaker, wider
reflection peaks indicate less ordered or smaller structures. Here, as
the cellulose content increases, the polyamide reflection peaks
become wider, indicating loss of crystallinity, while they move
closer to one another. The (100) reflection in PA66 arises from
intrasheet scattering, while the (010) and (110) reflections arise
from intersheet scattering. The d spacing for (100) and (010) planes
has been calculated from the diffractograms (software PDXL
(version 2.7.2.0), split Pearson VII peak shape function) and is
shown in Fig. 5(b). Interestingly, the d100-spacing is seen to
decrease with the addition of cellulose, meaning that the intrasheet
periodicity of the PA66 molecular chains decreases with increasing
cellulose. On the other hand, the d010-spacing increases with
increasing cellulose concentration, indicating that the intersheet
periodicity, i.e. the distance between the H-bonded chains, in-
creases. The above indicate a change in size of the crystallites, with
the addition of cellulose, more specifically the PA66 lamellae
become narrower with more space between the sheets, with
increasing cellulose. Since DSC does not give significant variation of
the crystallite size, the above means that the PA66 crystallites
comprise of fewer sheets, as the cellulose is increasing.
It should be mentioned that amorphous cellulose chains ho-
mogeneously distributed inside the amorphous part of PA66 will
result in a decrease of the melting point of the crystalline part,
especially when H-bonds are involved in the interactions [23,43],
further explaining the findings of DSC.
3.4. Mechanical performance
The mechanical properties of the blends were also characterized
and they are summarized in Fig. 6. The stress-strain curves are
presented in Fig. 6(a) and the data extracted from these curves are
shown in Fig. 6(b) and (c). Mechanical properties depend on both
the structure [44], as well as on any kind of interaction that might
exist between the two polymers [45], so in order to understand the
mechanical properties of the porous blends presented here, we
have to take under consideration both the blending of the two
polymers, as well as the porosity.
Here, the stress-strain (SeS) curves of the blends lie between
the two extreme curves of cellulose and PA66, revealing that the
blended films are less ductile than the pure ones. As shown in
Fig. 6(b), the Young modulus of the blended films, increases only
slightly as the cellulose content is increased, with respect to the
value of the pure PA66 films, however it does not reach the high
value of the cellulose film. The Young's moduli of the pure films, i.e.
PA66 and cellulose, are very different, with that of cellulose almost
an order of magnitude higher than that of PA66. The stiffness of the
blends then, lie between the two extremes, however they are very
close to the value of the PA66 film, even for high cellulose content.
This can be interpreted by considering that the stiffness of the
blends depends mostly on the moduli of the two polymers
constituting the blend, specifically on that of PA66, and not on the
structure, in accordance with previous results [45,46].
The tensile strain of the pure PA66 and cellulose, shown in
Fig. 6(c), are very different and that of the porous blends follow are
very close to that of cellulose. However, the strain of the porous
blends is lower than that of cellulose, and we attribute this decrease
to the porosity of the materials, that makes materials more sus-
ceptible to break at less elongation [44]. Similarly, despite the
similar values of the tensile stress of the pure PA66 and cellulose
blends, that of the porous blends decrease with increasing cellulose
content. This is attributed as much to porosity as to blending. It is
known that the fracture in porous films originates from local con-
centrations of stress at flaws or notches and it propagates easier
when pores are present [44]. In addition, it has been shown that
polymer blends with some degree of miscibility present monot-
onical change in tensile stress [45]. We can therefore conclude that
the mechanical properties of the PA66/cellulose porous blends
presented here are controlled from both their miscibility and their
porous structure.
3.5. Impedance spectroscopy
Fig. 7(a) and (b) show the Nyquist plots (-Zimg vs Zreal) of the
different polymer blend membranes, the pure cellulose, the PA66,
as well as two additional commercial porous materials (regener-
ated cellulose (RC) and PA66 membranes), used as references. Pure
cellulose, M75P25 and commercial RC membrane are presented in
Fig. 7(a) as obtained from the analysis of the impedance spectros-
copy data [28]. It is seen that the collected data form semi-circles,
according to IS models [47,48], with pure cellulose film and
M75P25 membrane having similar values. Similarly, in Fig. 7(b), the
Nyquist plots for M50P50, M25P75, PA66 and commercial PA66
membrane are shown as suppressed semi-circles, with similar
 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263 261

Fig. 6. (a) Stress-strain curves, (b) the Young modulus and (c) the strain and stress of
cellulose, PA66 and blends as a function of the PA66 concentration.

values among them. Values of polyamide-rich materials are higher

than those of cellulose-rich ones. Hence, the chemical nature of the
main component of the blends, i.e. cellulose or polyamide, controls
the response of the impedance with practically no intermediate
behaviour. Specifically, M50P50 is closer to PA66 than to MCC.
The dielectric constant or relative permittivity (εm) defines the
ability of a material to polarise in response to an applied electric
field in comparison to the vacuum. Even though common plastics
show low values of εm [49], both low and high dielectric constant
polymers are necessary in electronic industries. Assuming homo-
geneous conductors and plane-plate capacitors [50], the following
expression gives us the dielectric constant, εm:
Fig. 7. Nyquist plots for different samples. (a): Pure cellulose (,), M75P25 (*) and
regenerated cellulose (-); (b): M50P50 (D), M25P75 (V), pure PA 66 (◊) and com-
mercial PA 66 (A), (c) dielectric constant of cellulose, M50P50 and PA 66 samples (red)
in comparison to other conventional plastics and polymers (black). Inset: dielectric
constant of cellulose-PA 66 blends as a function of the cellulose content. (For inter-
pretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
Cm DXm
εm ¼ (6)
Sm ε0
262 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263

where DXm is the membrane thickness, Sm is the membrane area

used, Rm and Cm and the corresponding resistance and capacitance,
and ε0 is the vacuum permittivity. The calculated εm values for each
membrane are shown in the inset of Fig. 7(c). Pure PA66 and the
blends with low cellulose content, i.e. up to 50 wt% cellulose, have
similar εm values, close to 7.8. However, for pure cellulose mem-
branes, εm is increased up to almost four-fold (~30.0), while
M75P25 has an intermediate value of ca. 12.0. Fig. 7(c) also exhibits
a comparison of the dielectric constants of pure cellulose, M50P50
and pure PA66 samples with several conventional synthetic and
natural polymers such as polyethylene, ABS, PVC, Kapton, PDMS,
PVDF, neoprene, and regenerated cellulose [49]. Cellulose presents
the highest value of relative permittivity close to regenerated cel-
lulose. The dielectric constants of M50P50 and PA66 samples are
relatively low, with values between those of PVDF and neoprene.

3.6. Water uptake and salt permeability

Water uptake by a polymer membrane is a critical parameter in

water and salt transport properties. In Fig. 8, the water uptake is
depicted for the pure and the blended films. It is immediately seen
that water uptake is higher for the films with 3D porosity. Espe-
cially for the M50P50 film, which exhibits the highest porosity, the
water uptake is twice as high as for the rest of the samples, while
PA66 film presents the lower water uptake.
Fig. 9(a) depicts the salt permeability as a function of cellulose
content, where it is seen that with increasing cellulose content, Ps is
increased. This can be understood in terms of membrane structure.
Dense membranes, such as pure cellulose and M75P25, induce ion
transport through the polymeric chains, so the ions follow a
straight path between the two sides of the membrane. On the other
hand, in the case of porous membranes, such as M50P50 and
M25P75, the distance the ions have to travel is much longer due to
the 3D, non-continuous structure of the membrane, thus, reducing
the value of Ps. The two cases are depicted in the insets of Fig. 9(a).
Despite the lower porosity of M25P75 than M50P50, the salt Fig. 9. (a) Salt permeability as a function of the cellulose content. (b) Salt permeability
data of pure cellulose and M50P50 where other materials are showed for comparison
permeability is higher in M50P50. This is related to the higher reasons. The membranes described in the present article, are denoted with red. (For
hydrophilicity of cellulose, in comparison to that of PA66, since interpretation of the references to colour in this figure legend, the reader is referred to
hydrophilicity facilitates the flux of water and ions. Furthermore, as the web version of this article.)
seen in Fig. 8, M50P50 films uptakes 50% more water than M25P75,
and membranes that absorb more water are often more permeable
to water and salt [51]. cellulose and M50P50 with common materials currently used as
Fig. 9(b) presents a comparison of the salt permeability of membranes, such as hydroxyethyl methacrylate (HEMA) [52],
polyethersulfone [53], regenerated cellulose [54] and cellulose
diacetate [55]. Cellulose is close to membranes with high Ps, such as
regenerated cellulose and cellulose diacetate, while M50P50 can be
compared with membranes with low Ps, such as polyethersulfones.
This makes our PA66/cellulose porous blends potentially useful in
different membrane applications, since by tailoring the porosity of
the blends, one can tune the permeability to low values, useful
mainly in reverse osmosis for separation processes [56], or high
values, useful mainly in dialysis [57].

4. Conclusion

Cellulose-PA66 composites were fabricated, using TFA as com-

mon solvent for the microcrystalline cellulose and the PA66. The
composites exhibit a 3D, porous structure when the cellulose
concentration is lower than 50 wt%, which however disappears for
cellulose concentration higher than 50 wt%. Chemical analysis in-
dicates that the increase of cellulose content leads to the higher
amorphisation of PA66 and that possible interaction exists between
the amorphous part of the PA66 and the cellulose, via the H-bonds.
Fig. 8. Water uptake for the different blends. The mechanical properties of the PA66/cellulose porous blends
 E.L. Papadopoulou et al. / Polymer 120 (2017) 255e263
presented here depend on both the miscibility of the two polymers
as well as the porous structure of the films. It was found that the
stiffness of the blends is only slightly improved compared to that of
PA66, and much lower than the stiffness of pure cellulose. The
porosity of the films results in the decrease of their elongation and
the tensile stress, as expected, since porous structures are inclined
to break at shorter elongations with less stress. The composite films
were also characterized using impedance spectroscopy, where the
dielectric constant is found to depend on the relative concentration
of cellulose and polyamide. Water uptake showed maximum value
for the most porous film (M50P50). However a higher permeability
value for the M75P25 and the cellulose films was measured, since
the density of their structure allows the ions to travel faster be-
tween the two surfaces of the films. In conclusion, we have fabri-
cated cellulose-PA66 composite films with tailored porosity, via a
simple solution method. Tailoring the porosity results in tailoring of
the permeability, which allows these films to be of potential use for
membrane application for both low and high permeability.
Acknowledgments
Mr. Sergio Marras (Nanochemistry, IIT) is acknowledged for his
help with the PDXL software.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.polymer.2017.06.002.
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