Separation and Purication Technology 123 (2014) 229234

Contents lists available at ScienceDirect

Separation and Purication Technology

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

Structural and physicochemical investigation of ageing of ion-exchange

membranes in electrodialysis for food industry
R. Ghalloussi, L. Chaabane, C. Larchet, L. Dammak , D. Grande
Institut de Chimie et des Matriaux Paris-Est, UMR 7182 CNRS Universit Paris-Est, 2 Rue Henri Dunant, 94320 Thiais, France

a r t i c l e

i n f o

Article history:
Received 3 September 2013
Received in revised form 9 December 2013
Accepted 11 December 2013
Available online 8 January 2014
Keywords:
Ion-exchange membranes
Electrodialysis
Ageing
EDX
SEM
Conductivity

a b s t r a c t
The ageing mechanism of ion-exchange membranes (IEMs) used in electrodialysis for food industry was
investigated through the use of several analytical techniques. Structural and physicochemical properties
of two different IEMs, i.e. a cation-exchange membrane (CEM) and an anion-exchange membrane (AEM)
were studied. The comparison of conductivity, thickness, water uptake, ion-exchange capacity and contact angle values as well as SEM micrographs and energy dispersive X-ray (EDX) spectra between new
and used samples showed a signicant degradation of membranes after 2 years of use in an electrodialysis module.
The CEM became denser and more hydrophobic, while the thickness of the AEM increased and the
membrane became more hydrophilic. A signicant degradation in the polymer matrix of both membrane
types was found. The used membranes lost a part of their ion-exchange sites, and their specic electrical
conductivity signicantly decreases. To explain the important variations of equilibrium properties, we
have applied the microheterogeneous model.
2013 Elsevier B.V. All rights reserved.

1. Introduction
The lifetime of dense membranes has been improved signicantly over the past two decades. However, very few studies have
been conducted to develop reliable protocols for characterization
and control of these membranes during their life cycles. Often,
the manufacturers are resigned to observing the drop in membrane
and process performances, which preceded the outright replacement of the modules. Thus, the ageing mechanisms of materials
and the factors inuencing their durability remained very little
known.
Currently, one of the most important applications of
ion-exchange membranes (IEMs) is the electrodialysis (ED) for
desalination of saline water, demineralization of whey, as well as
acid and alkali recovery [13]. Moreover, new applications of ED
have been identied in water and waste treatment [4], in food
industry [5] including dairy [6], fruit juice [7], sugar [8], and wine
production [9].
The evaluation of the IEM lifetime is a very important element
in the control of the ED operations, as the loss of their physicochemical and separative properties is usually accompanied by
lower yields and increased costs, due to the growth of energy consumption. In this context, the understanding of ageing processes
occurring in IEMs used in ED for food industry applications, and
Corresponding author. Tel.: +33 149781173.
E-mail addresses: dammak@u-pec.fr, dammak@icmpe.cnrs.fr (L. Dammak).
1383-5866/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2013.12.020

the investigation of their long-term behavior are necessary to enhance the progress of this advantageous technology.
Generally, the main causes associated with the deterioration of
membrane properties as discussed in the literature are membrane
fouling and poisoning [10,11]. The fouling of permselective membranes is one of the major problems in electrodialysis and can be
due to (i) build up of scale by hydroxide formation of divalent
and trivalent ions, (ii) surface blocking by proteins or colloidal
matter, or (iii) membrane poisoning by tensio-active agents [12].
Fouling increases cell resistance, decreases IEM permselectivity,
and could alter the membrane structure (reversible and irreversible fouling) [1315].
Accordingly, published information on IEM ageing remains
scarce, especially for membranes used in food industry ED applications. This work lies within the scope of a research project aiming
to explore the effects, causes, and mechanisms of IEM ageing in ED
for food industry applications [1620]. In our more recent paper
and that of Garcia-Vasquez et al., ageing of cation-exchange membranes (CEMs) [19] and anion-exchange membranes (AEMs)
[19,20] was investigated in two different applications of industrial
ED. Membranes suffered a signicant decrease in the ion-exchange
capacity and an important damage in the functional polymer
chains, when performing ED for the treatment of organic acids
[19], in which diluted oxidizing solutions might be used to clean
and sanitize the ED stack. On the other hand, no signicant loss
of the ion-exchange capacity or degradation of the functional polymer chains was detected on membranes used for whey demineral-

230

R. Ghalloussi et al. / Separation and Purication Technology 123 (2014) 229234

ization [20]; ageing comes from a progressive loss of the polymer

binder, thus leading to the formation of non-charged pores that
change the permselectivity and the mechanical properties of the
membranes.
In this paper, we will focus on the evolution of structural and
physicochemical properties of a cation-exchange membrane
(CEM) and an anion-exchange membrane (AEM) after two years
of use in an ED process for food industry. This evaluation is investigated by means of several analytical techniques. This investigation is based on the comparison of structural, static and dynamic
properties of IEMs before and after ED use in order to identify
the main origins of the degradation observed.
2. Experimental
2.1. Ion-exchange membranes (IEMs)
Neosepta membrane are made of polystyrene crosslinked with
divinylbenzene (DVB) and reinforced by a PVC cloth. For this study,
two membranes (Neosepta brand) were provided by Eurodia
Industry S.A.: a CEM which contain negatively charged groups

(SO
3 ) and an AEM containing positively charged groups (NH3 )
consisted of a sample of a new membrane and another one retired
from an ED module after two years of use.
We will use the following notation to name them: CEMN (new
CEM), CEMU (used CEM), AEMN (new AEM) and AEMU (used AEM).
We note that before any measurement, it was necessary to
condition the new and aged samples in order to stabilize their
physicochemical properties and remove any impurities that may
come from their manufacturing process. The French standard
NF-45-200 [16] was followed to realize this treatment.
2.2. Equilibrium characteristics
2.2.1. Ion-exchange capacity
The ion-exchange capacity is the number of functional sites per
gram of dry membrane. This parameter was determined following
the French standard NF X 45-200 [21]. The CEM sample was placed
in a 1 M HCl solution. The sample was then abundantly washed
with water; it was converted into the Na+ form by soaking them
in a solution obtained from mixing 230 mL of a 0.1 M NaCl and
20 mL of a 0.1 M NaOH solutions, during 2 h at 25 C. The ion-exchange capacity (EC) was determined by titration of the remaining
OH ions and expressed as the amount of sorbed H+ (meq g1 dry).
The AEM sample was placed in a 0.1 M HCl solution. The sample
was also abundantly washed with water; it was immersed in a
1.0 M HNO3 solution during 12 h at 25 C. The ion-exchange capacity was determined by the chloride content in the equilibrium
solution.

value was averaged from measurements at 10 different locations

on the effective surface region of the membrane.
2.2.4. Contact angle
The measurements of the contact angle values were performed
using a FM40 EasyDrop device from Krss. The images of a water
drop at the surface of the membrane were captured by a high resolution camera, and they were then processed by the Wingoutte
software to determine the contact angle value using interpolation
methods.
The measurements were repeated 5 times at different spots of
the dry membrane at room temperature (just the bound water
was remaining). The contact angle was determined as an average
value of 5 measurements.
2.2.5. Alternating current conductivity
To measure the membrane conductivity, the experimental
assembly (Fig. 1) consisted of a clip-type cell connected to a conductimeter CDM92 (RADIOMETER-TACUSSEL) and a water bath
at 25 1 C [22].
The determination of membrane conductance Gm needed two
measurements, i.e. one without the membrane (G1) and another
G2
one with the membrane (G2), to deduce the value Gm GG11G
Using
2
the value of the membrane thickness (Tm) and the electrodes section area (A = 1 cm2), the membrane conductivity was calculated
asjm Gm  TAm :
The conductivity of the two pairs of membranes was measured
in NaCl solutions at different concentrations ranging from 102 to
0.5 mol L1.
2.3. Structural characteristics by SEM and EDX
Samples used for the structural investigation were vacuum
dried overnight at 40C, before analysis. Scanning electron microscopy (SEM) images were obtained from Pt/Pd coated samples with
an accelerating tension of 3 keV using a LEO 1530 microscope. The
surface elemental composition of the samples was also determined
by energy-dispersive X-ray (EDX) spectroscopy with a 10 mm2 germanium diode as an X-ray detector (Imix, Princeton Gamma-Tech)
attached to the SEM equipment.

2.2.2. Water uptake

Samples were separated from the stabilization solution and the
excess of external liquid was removed by placing them between
two foils of lter paper and pressing slightly for the measurement
of the wet mass Wa. The dry mass Wb was obtained by drying the
samples at 60 C for 24 h. The water uptake was then found as follows: %W W aWW b  100:
b
Before measurement, the membranes were soaked during 24 h
at 25 C in an electrolyte solution (0.1 M NaCl for CEMs and 0.1 M
HCl for AEMs).
2.2.3. Membrane thickness
The membrane thickness (Tm) was measured using a Kfer
Thickness Dial Gauge specially devised for plastic lm thickness
measurements with a resolution of 1 lm. The membrane thickness

Fig. 1. Experimental device for the ac measurement of membrane conductivity.

R. Ghalloussi et al. / Separation and Purication Technology 123 (2014) 229234

2.4. Results and discussion

2.4.1. Static characteristics
The French standard NF 45-200 [21] was followed to determine
the main equilibrium characteristics of the different membranes
studied (Table 1).
Table 1 shows a signicant drop of the ion-exchange capacities
of both membranes after 2 years of use in ED treatment of solutions containing weak organic acids, in a food industry application.
The CEM specimen shows a dramatic variation in its contact angle
(+108 %) and ion-exchange capacity (71%), but it displays a moderate decrease in its water content (16%) and thickness (9%).
The AEM appears to be the most affected membrane with the
decrease in ion-exchange capacity (84%) and contact angle
(25%), accompanied by a large increase in water content (+40%)
and thickness (+130%).
The contact angle of CEM increases signicantly after ED operation, thus showing that the membrane becomes less hydrophilic.
This is consistent with the decrease in the water content. The loss
of water and the increase in surface hydrophobicity apparently
arise from the reduction in the concentration of active functional
sites resulting from their detachment. In contrast, the decrease in
the contact angle of the used AEM shows that the membrane
becomes more hydrophilic. This is conrmed by an important
increase in the water content and in the membrane thickness.
Taking into account that the ion-exchange capacity decreases, this

Table 1
Static characteristics of the studied membranes: ion-exchange capacity (EC), water
uptake (W (%)), thickness (Tm) and contact angle (h).
Membranes
1

EC (meq g
W (%)
Tm (lm)
h ()

of dry IEM)

CEMN

CEMU

AEMN

AEMU

2.66
28.2
176
38 2

0.77
23.7
160
79 2

1.45
28.7
148
69 2

0.23
40.3
344
52 2

The inaccuracy of measurements is estimated to be equal to 5%

231

effect might be due to the sorption of highly hydrophilic substances, which could be organic acids with hydrophilic groups,
such as carboxyl or hydroxyl ones.

2.4.2. Structural characteristics

Figs. 2 and 3 show SEM micrographs of CEM and AEM before
and after use in ED process.
As it could be seen, the surface of a fresh Neosepta membrane
was smooth and homogeneous. The CEM sample had a at and
fairly homogeneous surface, even at the nanoscopic length scale.
The low magnication image revealed some cracks formed in the
used CEM. We might suppose that these cracks existed before drying the sample or they were formed as a consequence of it.
Concerning the AEM, the surface and the cross-section of the
used AEM showed important structural defects. They gave evidence of the existence of some micrometric heterogeneity on the
surface.
The results of EDX analyses for the CEM sample are displayed in
Fig. 4, and for AEM in Fig. 5. For each IEM, an area of 1 lm2 of functional polymer was considered (the membrane cloth was avoided).
The analyzed elements were oxygen, sodium, magnesium, sulfur,
chlorine and calcium.
Fig. 4 shows a signicant decrease in the intensity of the peaks
corresponding to sulfur and sodium in the used membranes. This
conrms that some of the sulfonic functional sites of CEMU (here
+
in balance with sodium: SO
3 Na ) are completely removed from
the membrane. The magnitude of this decrease is comparable to
that of EC (see Table 1). It is noteworthy that the Cl content decreases with membrane ageing for the CEM and the AEM. This
should result from a decrease in the PVC content, whose segments
detach from the membrane due to the erosion of the ion-exchange
polymer [23] forming a continuous phase in Neosepta membranes and weakening junctions between interpenetrating ion-exchange and PVC polymers. While the content of S decreases in the
CEM, testifying the loss of ion-exchange capacity, its content increases in the AEM, due to the presence of this element in solutions
under ED treatment.

Fig. 2. SEM micrographs of CEMN-cross section (a), CEMU-cross section (b), CEMN external surface (c) and CEMU-external surface (d).

232

R. Ghalloussi et al. / Separation and Purication Technology 123 (2014) 229234

Fig. 3. SEM micrographs of AEMN-cross section (a), AEMU-cross section (b), AEMN external surface (c) and AEMU-external surface (d).

Fig. 4. EDX analysis of the membrane surface of the CEMN and CEMU.

Fig. 5. EDX analysis of the membrane surface of the AEMN and AEMU.

2.4.3. Dynamic characteristics

The values of the membrane conductivity in 0.1 M NaCl for the
IEMs investigated are shown in Fig. 6 before and after two years of
use in ED.

Fig. 6. The ionic conductivity of the CEM and the AEM, ( ) new membranes and (j)
used membranes.

In all cases, we observe a decrease in the conductivity between

the new and used samples, which may generally be explained by
the loss of ion-exchange capacity. In the case of the CEM, the decrease in the value of ion-exchange capacity (71%) and conductivity occur to a similar extent. However, in the case of the AEM,
an important loss in the ion-exchange capacity (84%) does not
lead to a comparable decrease in conductivity. Apparently this
should be due to the difference in microstructure changes of
CEM and AEM during their use in ED. In order to try to identify
these changes in both cases, we applied the well-established
microheterogeneous model [24,25].
This model correlates membrane physicochemical properties
with its kinetic and structural parameters. Namely, a simple equation linking the membrane conductivity jm to the external electrolyte conductivity, js, allows for the determination of the volume
fractions f1 and f2 of the membrane gel phase and the electrically
neutral solution lling the intergel spaces, respectively
(f1 + f2 = 1). Let us write this equation in the logarithmic form:

log jm f1 log jg f2 log js ;

where jg is the conductivity of the gel phase.

R. Ghalloussi et al. / Separation and Purication Technology 123 (2014) 229234

233

Fig. 7. log jm vs log js of the CEMN (j) and CEMU ().

Fig. 9. Value of f2 of the CEM and AEM, ( ) new membrane and (j) used
membrane.

Fig. 8. log jm vs log js of the AEMN (j) and AEMU ().

According to this model, two phases in an IEM can be

distinguished. The gel phase is a nanoporous medium, globally
electroneutral, which contains functional sites, mobile ions, the
polymer matrix, and water. The interstitial electroneutral solution,
which is assumed to be identical to the outer equilibrium solution,
lls the inner parts of meso- and macro-pores as well as ssures
and cavities (= intergel spaces). Eq. (1) holds in the range of concentrations from 0.1 ciso to 10 ciso [25] (ciso is the isoconductance
concentration at which the specic conductivity of the membrane
and that of the external solution are the same).
The slope of the log jm vs. log js curve gives the f2 value. Figs. 7
and 8 present the experimental dependence of log jm on log js
found for the fresh and the used CEM and AEM, respectively, equilibrated with NaCl solutions (0.1 molL1).
The f2 values for fresh and used samples are given in the histogram of Fig. 9.
The CEM shows a decrease in the f2 value. It may be explained
by a lower swelling of the membrane after its use in ED. On the
contrary, the f2 value for the AEM increases after its use. This trend
is in good agreement with the variations of water content and
thickness of this membrane.
In both cases of CEM and AEM, their use in ED treatment of food
industry solutions containing organic acids results in the loss of
ion-exchange capacity and decrease in electrical conductivity. Such
a decrease leads to increasing power consumption and a deterioration of economic efciency of the ED process. However, the mechanism of cation-exchange and anion-exchange membrane ageing is
different.
In the case of CEM, EDX analysis shows a signicant loss of sulfonic functional sites, which are strongly hydrophilic. This loss
leads to a decrease in the water content and the membrane

Fig. 10. Possible structure of AEM: (a) before ED, (b) at the end of its lifetime in ED
for food industry. 1: macro-defects of structure, 2: nanoporous medium, 3:
nanopore lled with the charged solution, 4: non-selective cavities left by the lost
PVC.

thickness. It also leads to an increase in the contact angle value.

Hence, the membrane becomes denser and its pores narrower,
which is manifested by a decrease in the volume fraction of intergel solution, f2. Lower ion-exchange capacity and narrower pores
result in a decrease in the concentration and mobility of counterions, and therefore, in a loss of the specic conductivity, jm. A lower
ion-exchange capacity leads to increasing sorption of co-ions,
which contribute to higher conductivity, but causes a loss in
permselectivity.
The apparent scenario of changes in structure of an AEM during
its operation in ED of food industry is shown in Fig. 10. A fresh
membrane contains a small amount of macropores and a nanoporous medium providing selective transport to the membrane. The
major part of solution within nanopores is charged, while its

234

R. Ghalloussi et al. / Separation and Purication Technology 123 (2014) 229234

central part is electrically neutral. This solution together with the

solution in macropores forms the intergel solution with volume
fraction f2. During ED operation, organic foulants (such as amino
acids) form colloid associates located within the nanopores [10]
and can foul them, thus reducing the mobility of ions there. Such
organic colloids occupy the central part of a nanopore pushing
out the electroneutral solution. As a result, the volume fraction
of the charged solution counterbalancing the charge of the pore
walls increases that leads to increasing permselectivity. In fact,
the concentration of mobile counterions in the charged solution
forming the interfacial double electrical layer (DEL) is much higher
than that of co-ions. In some cases, the DELs formed at the pore
wall and at the colloid particle surface may overlap providing
highly selective transport of counterions.
A similar nanoporous structure with nanoparticles immobilised
within membrane pores and leading to increased permselectivity
was recently described by Yaroslavtsev et al. [26,27] (the case of
SiO2, ZrO2 and other nanoparticles in Naon-type membranes).
3. Conclusion
This paper provides an insight into the understanding of ageing
of a CEM and an AEM used in ED processes for the food industry
involving organic acids.
We can conclude that a part of ion-exchange sites of both types
of membranes is lost; their specic electrical conductivity decreases. However, the CEM is generally more robust and resistant
than its anion-exchange counterpart. The structure and properties
of CEM and AEM vary in different ways. The CEM becomes denser,
its water content and thickness decrease, and the surface becomes
more hydrophobic. The loss of ion-exchange sites leads to increasing concentration of co-ions in CEM and deterioration of its
permselectivity.
For the AEM, the surface hydrophilicity increases since its water
content and its thickness increase essentially in the course of ED.
This behaviour can be explained by sorption of organic colloidal
particles within membrane nanopores. As these particles are
generally hydrophilic, they attract water which leads to higher
swelling. At the same time, these particles replace electroneutral
solution in the pore centre. As a result, the effective radius of ion
conducting channels decreases, and the double electrical layers
occupy a more important volume fraction of the pore solution that
favours permselectivity. However, the higher swelling of AEM
leads to the rupture of some bonds and polymer chains. As a result,
structure macro-defects (ssures, cavities, caverns) lled with
external solution appear in the membranes. In the long-term run,
these defects may form through non-selective passages leading
to fully unt membranes.
Acknowledgment
A part of this study was carried out within the French-Russian
Associated International Laboratory Ion-Exchange Membranes
and Related Processes (LIA-MEIPA).
References
[1] T. Sata, T. Sata, W. Yang, Studies on cation-exchange membranes having
permselectivity between cations in electrodialysis, J. Membr. Sci. 206 (2002)
3160.

[2] Y. Kubuchi, H. Motomura, Y. Noma, F. Hanada, Application of ion-exchange

membranes to the recovery of acids by diffusion dialysis, J. Membr. Sci. 27
(1986) 173.
[3] T. Sata, New application of ion-exchange membranes, in: J. Kohovec (Ed.),
Macromolecules, VSP, Utrecht, The Netherlands, 1992, p. 451.
[4] R.K. Nagarale, G.S. Gohil, V.K. Shahi, Recent developments on ion-exchange
membranes and electro-membrane processes, Adv. Colloid Interface Sci. 119
(2006) 97130.
[5] M. Fidaleo, M. Moresi, Electrodialysis applications in the food industry, Adv.
Food Nutr. Res. 51 (2006) 265360.
[6] L.J. Andrs, F.A. Riera, R. Alvarez, Skimmed milk demineralization by electrodialysis: conventional versus selective membranes, J. Food Eng. 26 (1995) 57
66.
[7] E. Vera, J. Sandeaux, F. Persin, G. Pourcelly, M. Dornier, J. Ruales, Modeling of
claried tropical fruit juice deacidication by electrodialysis, J. Membr. Sci. 326
(2009) 472483.
[8] A. Elmidaoui, F. Lutin, L. Chay, M. Taky, M. Tahaikt, R. AlaouiHad, Removal of
melassigenic ions for beet sugar syrups by electrodialysis using a new anionexchange membrane, Desalination 148 (2002) 143148.
[9] F. Goncalves, C. Fernandes, P.C. Dos Santos, M. Norberta de Pinho, Wine tartaric
stabilization by electrodialysis and its assessment by the saturation
temperature, J. Food Eng. 59 (2003) 229235.
[10] T. Sata, Ion exchange membranes: preparation, characterization, modication
and application, Rev. Soc. Chem. (2004) 314319.
[11] Y. Tanaka, Ion exchange membranes: fundamentals and applications, chapter
14 membrane deterioration, Membr. Sci. Technol. 12 (2007) 293317.
[12] L. Bazinet, F. Lamarche, D. Ippersiel, D. Montpetit, J. Amiot, Identication of
skim milk electroacidication fouling: a microscopic approach, J. Colloid
Interface Sci. 237 (2001) 6269.
[13] F.G. Donnan, The theory of membrane equilibrium in presence of a nondialysable electrolyte, Z. Elektrochem. 17 (1911) 572.
[14] E. Korngold, in: G. Bedford (Ed.), Synthetic Membrane Process, Academic Press,
New York, 1984, pp. 191220.
[15] C.
Gavach,
Symposium
sur
les
applications
alimentaires
de
llectrodialyse, Foundation des Gouverneurs, Saint-Hyacinthe, Que., 23
et 24 Mars, 1999.
[16] L. Dammak, C. Larchet, D. Grande, Ageing of ion-exchange membranes in
oxidant solutions, Sep. Purif. Technol. 69 (2009) 4347.
[17] R. Ghalloussi, W. Garcia-Vasquez, N. Bellakhal, C. Larchet, L. Dammak, P.
Huguet, D. Grande, Ageing of ion-exchange membranes used in
electrodialysis: investigation of static parameters, electrolyte permeability
and tensile strength, Sep. Purif. Technol. 80 (2011) 270275.
[18] R. Ghalloussi, W. Garcia-Vasquez, L. Chaabane, L. Dammak, C. Larchet,
N. Bellakhal, Decline of ion-exchange membranes after utilization in
electrodialysis for food applications, Phys. Chem. News 65 (2012) 66
72.
[19] R. Ghalloussi, W. Garcia-Vasquez, L. Chaabane, L. Dammak, C. Larchet, S.V.
Deabate, E. Nevakshenova, V. Nikonenko, D. Grande, Ageing of ion-exchange
membranes in electrodialysis: a structural and physicochemical investigation,
J. Membr. Sci. 436 (2013) 6878.
[20] W. Garcia-Vasquez, L. Dammak, C. Larchet, V. Nikonenko, N. Pismenskaya, D.
Grande, Evolution of anion-exchange membrane properties in a full scale
electrodialysis stack, J. Membr. Sci. 446 (2013) 255265.
[21] AFNOR, French standard NF X 45-200 (1995).
[22] R. Lteif, L. Dammak, C. Larchet, B. Auclair, Conductivit lectrique
membranaire: tude de leffet de la concentration, de la nature de
llectrolyte et de la structure membranaire, Eur. Polym. J. 35 (1999) 1187
1195.
[23] N.D. Pismenskaya, V.V. Nikonenko, N.A. Melnik, K.A. Shevtsova, E.I. Belova, G.
Pourcelly, D. Cot, L. Dammak, C. Larchet, Evolution with time of
hydrophobicity and micro relief of a cation-exchange membrane surface and
its impact on over limiting mass transfer, J. Phys. Chem. B 116 (2012) 2145
2161.
[24] N.P. Berezina, N.A. Kononenko, O.A. Dyomina, N.P. Gnusin, Characterization of
ion-exchange membrane materials: properties vs structure, Adv. Colloid
Interface Sci. 139 (2008) 328.
[25] V.I. Zabolotsky, V.V. Nikonenko, Effect of structural membrane inhomogeneity
on transport properties, J. Membr. Sci. 79 (1993) 181198.
[26] S.A. Novikova, E.Y. Safronova, A.A. Lysova, A.B. Yaroslavtsev, Mendeleev
Commun. 20 (2010) 156157.
[27] V.V. Nikonenko, A.B. Yaroslavtsev, G. Pourcelly, Ion transfer in and through
charged membranes, Structure, properties, theory, in: A. Ciferri, A. Perico
(Eds.), Ionic Interactions in Natural and Synthetic Macromolecules, John Wiley
& Sons, Inc., 2012, pp. 267336. Chapter 9.