Polym. Bull.

DOI 10.1007/s00289-015-1531-0
ORIGINAL PAPER

Ion-selective interpenetrating polymer networks

supported inside polypropylene microporous
membranes for the removal of chromium ions
from aqueous media
Yesid Tapiero1 Julio Sanchez1 Bernabe L. Rivas1

Received: 9 May 2015 / Revised: 30 August 2015 / Accepted: 29 September 2015

Springer-Verlag Berlin Heidelberg 2015

Abstract The ion-exchange properties of interpenetrating polymer networks (IPNs)

have been studied to provide metal-ion transport with high selectivity. Polypropylene
(PP) membranes incorporating poly[(ar-vinylbenzyl) trimethylammonium chloride],
P(ClVBTA), poly[2-(acryloyloxy)ethyl]trimethylammonium chloride] P(ClAETA),
poly(acrylic acid) P(AA), poly(2-acrylamidoglycolic acid) P(AGA), poly(glycidylmethacrylate-N-methyl-D-glucamine) P(GMA-NMG), poly(2-acrylamido-2-methyl1-propane sulfonic acid) P(AMPS), and poly[sodium (styrene sulfonate)], P(SSNa)
were modified via an in situ radical-polymerization. The surface of PP was activated by a hydrophilic grafted polyelectrolyte and then pressure injection was used for
impregnation of the reactive solution in the membrane. The following conditions were
varied: the functional monomer, grafted polyelectrolyte, and cross-linked concentration. The modified PP membranes were characterized using SEM/EDS, FT-IR,
electrokinetic potential, and Donnan dialysis for the chromium ion transport. The
modified membranes exhibited hydrophilic character with a water-uptake capacity
between 15 and 40 % and a percentage of modification between 2.5 and 5.5 % in
comparison with the behavior of the unmodified polypropylene membrane as the blank
probe. Hexavalent chromium ions were efficiently transported by the modified
membranes containing P(ClVBTA) (61.2 %) and only 5.8 % of trivalent chromium
were extracted at pH 3.0 using a 1 mol/L NaCl solution as the extraction reagent.
Similarly, Cr(III) transport using membranes modified with P(SSNa) achieved 42.1 %
extraction at pH 3.0 using 1 mol/L NaCl as the extraction reagent and 2.5 % extraction
was achieved for Cr(VI). Unmodified PP membrane shows Cr(VI) extraction percentage between 1.6 and 3.1 %, and Cr(III)extraction percentage between 2.3 and
2.6 %.
& Bernabe L. Rivas
brivas@udec.cl
1

Polymer Department, Faculty of Chemistry, University of Concepcion, Casilla 160-C,

Concepcion, Chile

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Keywords Polypropylene  Ion exchange  Donnan dialysis  Interpenetrating

polymer networks  Chromium  Extraction  Membranes

Introduction
A major environmental problem is water pollution, caused principally by industrial
development. Many industrial processes, such as surface plating and chromium
electro-plating (decorative and hard plating) and the manufacturing of inks, paints,
plastics, stainless steel handwork and other alloys, concrete, bricks, photographic
material, and other chemicals process use chromium ions as a raw material.
Chromium ions may also enter drinking water from the corrosion inhibitors used in
water pipes and containers [1, 2]. The main ion species of chromium in the
environment are Cr(III) and Cr(VI). For example, the Cr(VI) depending on its
concentration and exposure period can cause serious health problems such as cancer
[3, 4]. Additionally, the Cr(VI) is soluble in water over all pH ranges and does not
depend on the concentration. Nevertheless, the speciation of Cr(VI) depends on the
pH and concentration: for example, at basic pH values, it exists as chromate
(CrO42-) ions, and at acidic pH values, it exists as an acid chromate (HCrO4-) or
dichromate (Cr2O72-) ion or a mixture, depending on the concentration.
The Cr(III) ion is essential for life. However, at certain concentrations, the Cr(III)
ion can be toxic [5]. Additionally, the main Cr(III) species that dissolves in water at
0
acidic pH values below 3.6 are Cr(OH)?
2 , Cr(OH)3, and Cr(OH)4 chromyl ions.
When the pH values are higher, Cr(III) precipitates as Cr(OH)3 9 nH2O [6].
The World Health Organization (WHO) requires a maximum concentration limit
of 0.05 mg/L for Cr(VI) or Cr(III) [7]. The techniques for the removal and recovery
of Cr(VI) are of increasing interest in the scientific area. Several representative
methods for the removal of Cr(VI) from polluted solutions are precipitation,
adsorption, ion-exchange [8, 9] membrane technologies (reverse osmosis, ultrafiltration, nanofiltration, dialysis, diffusion dialysis, Donnan dialysis, electrodialysis,
liquid, emulsified, and supported membranes) [1012]. However, a difficult problem
arises for the use of membrane technology when ions are of the same valence and
are close in nature or size.
Taking into account the Donnan dialysis, this technique is attractive because it is
an economical and simple process. It utilizes the difference in the electrochemical
potential on both sides of the membrane as the driving force [13]. Donnan dialysis
has applications in many areas, such as chemical analysis for pre-concentration,
extraction processes, hydrometallurgy, and separating acids from their salts [14, 15],
radioactive-flow deacidification, the removal of copper and zinc using commercial
cationic membranes, the removal of inorganic anions such as fluoride, nitrate,
bromate, and borate from drinking water, and the removal of Cr(VI) ions using
commercial anion-exchange membranes such as SB-6470, AFN, ACM, and Raipore
1030 [16]. The efficiency of the process depends on selecting a suitable functional
work membrane.
An alternative way of modifying the microporous support is by the formation of
interpenetrating polymer networks (IPN) because it makes possible to develop new

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materials that have definitive properties. Therefore, these materials are important in
both fundamental and applied investigations. The process is fast and simple way for
many polymer systems.
IPN architectures are formed when two or more polymer networks are partially
and non-covalently crosslinked on the molecular scale. These IPNs cannot be
separated by link breakages via chemical methods [17]. Active ion-exchange
membranes are ideally developed from chemically, mechanically, and thermally
stable, commercial porous materials. Several examples of commercial, disposable,
microporous membranes are polypropylene (PP) or polyethylene. These polyolefin
materials are attractive due to the stability and good thermal, mechanical, and
chemical properties.
Also, the poly(ar-[(vinylbenzyl)trimethylammonium chloride] P(ClVBTA), and
the poly([2-(acryloyloxy)ethyl]trimethylammonium chloride) P(ClAETA) are an
effective cation exchange polymer materials used in removal processes of
chromium ions [2]. The poly(sodium(styrenesulfonate)) P(SSNa), and the poly(2acrylamido-2-methyl-1-propane sulfonic acid) P(AMPS) are good anion exchange
polymer materials employed in different water treatment processes. The
poly(acrylic acid) P(AA), poly(2-acrylamidoglycolic acid) P(AGA), and poly(glycidyl methacrylate-N-methyl-D-glucamine) P(GMA-NMG) are efficient chelating
polymers materials used in ion removal [18, 19].
The aim of this work is to modify polypropylene PP membranes with
interpenetrating P(ClVBTA), P(GMA-NMG), P(AA), P(AGA), P(ClAETA),
P(AMPS), and P(SSNa) networks and to probe these membranes for Cr(III) and
Cr(VI) ion transport via Donnan dialysis from a feed mixture in acidic media.

Experimental
Materials
Sodium styrenesulfonate (SSNa, Aldrich), N-methyl-D-glucamine (NMG, Aldrich),
2-acrylamidoglycolic acid monohydrate (AGA, Aldrich), 2-acrylamido-2-methyl-1propane sulfonic acid (AMPS, Aldrich), ar-[(vinylbenzyl)trimethylammonium
chloride] (ClVBTA, Aldrich), N,N0 -methylenebisacrylamide (MBA, Aldrich),
sodium acrylic acid (AA, Aldrich), glycidyl methacrylate (GMA, Aldrich), [2(acryloyloxy)ethyl]trimethylammonium chloride (ClAETA, Aldrich), and ammonium persulfate (APS, Merck) were employed for the IPN synthesis.
Microporous, isotactic PP membranes were employed (0.6-lm pore size, AN06
Merck Millipore), and hydrophilic PVDF membranes (0.22-lm pore size, Millipore
Durapore type GV and 0.45-lm pore size, Millipore Durapore type HVLP) MGV
and MHVLP were also used. For the activation of the PP surface, the reagents
employed were 15-kDa polyvinyl alcohol (PVA, Merck), 15-kDa poly(ethyleneimine) (PEI, Aldrich), ethanol (Merck), and Type I deionized water from Thermo
Fisher TKA scientific. A stirred-cell filtration unit (Millipore, model 8050) was used
to inject the reactive solution pressure into the porous PP membrane. An aluminum

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flat-reactor was used for the radical polymerization of the functional IPNs. A UB-10
pH/mV meter from Denver instrument was used to measure the pH solution.
HNO3 (Merck), and NaOH (Merck) were used to control the pH. K2Cr2O7
(Merck) and Cr(NO3)3 9 9H2O (Merck) were the chromium sources. NaCl (Merck)
was the extraction reagent.
A Cary 100 Scan UVVisible spectrophotometer from Varian was used to
directly measure the Cr(VI) and Cr(III) ion concentrations. The Cr(VI) ion was
measured at 350 nm in a solution of pH 3.0. The Cr(III) ion concentration was
measured at the wavelength 573 nm for an acidic pH, this wavelength is only
selective to the Cr(III) [20, 21]. At wavelength 300 nm the Cr(III) and Cr(VI)
absorb energy, and can cause mistakes in the measurement. Origin Pro 8 software
was used to do the graphical profiles.
Synthesis of GMA-NMG
The GMA-NMG monomer was obtained following the method proposed by Toledo
et al. [22]. First, 60 mL of an aqueous solution (0.83 mol/L) of N-methyl-Dglucamine was added into a three-neck round bottom flask. Then, 6.8 mL
(50.0 mmol/L) of GMA was slowly added to the NMG solution. The reaction
was incubated for 5 h at 70 C with powerful stirring. The reaction was kept under
reflux with constant stirring for 5 h. At the end of the reaction; only one aqueous
phase was observed. By extraction with diethyl ether, the unreacted GMA was
removed, and the functionalized monomer GMA-NMG remained in the aqueous
phase.
Synthesis of IPNs inside of the membranes
The membranes were washed with an aqueous mixture of 50 % w/w ethanol to
eliminate all waste and wet the pores.
Hydrophilization process for the polypropylene surface
The PP membranes were coated with a hydrophilic polyelectrolyte (PVA or PEI) by
a thermochemical grafting procedure [23, 24]. The polyelectrolyte [PVA or PEI,
1000 mg/L], 1.5 9 10-1 mol/L NaCl and an initiator reagent [1 mol%, APS] in a
10 mL reaction solution were passed through the membrane. The samples were
dried in an oven at 60 C for 12 h. Finally, the membranes were washed with water
four times. The samples were dried in an oven at 50 C and left in a silica dryer for
24 h. The membrane codes are MPVA and MPEI.
Interpenetrating polymer network formation by pressure-injection method
A stirred-cell filtration unit was used with nitrogen gas and a pressure of 1 bar. The
functional monomer, crosslinking reagent (MBA), and initiator agent (APS) in a
20-mL reaction solution were passed through the membrane. Table 1 shows the
experimental design for the IPN formation. Only one injection was done.

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Table 1 Experimental design
of the (IPN)s synthesis using
7 9 10-1 mol/L of each
functional monomer

Sample code of the polymer network

MP(ClVBTA)

Mol% (MBA)
6

Type
Cationic

10
15
MP(ClAETA)

6
10
15

MP(AA)

Weak acid

10
15
MP(AGA)

6
10
15

MP(SSNa)

Anionic

10
15
MP(AMPS)

6
10
15

MP(GMA-NMG)

Chelating

10
15

Polymerization
Figure 1 shows the scheme of IPN-formation process. The in situ free-radical
polymerization was performed inside the membrane pores and on the surface at
70 C for 24 h. APS, 1 mol % was employed as initiator.
Characterization
Physical properties
Percentage of modification The percentage of modification was gravimetrically
determined. For the first step, the unmodified dry membranes were weighed. These
dry membrane samples were weighed again after the modification process. The
percent modification (% PM) was determined from Eq. 1:
%PM

wf  w0
 100 %;
w0

where wf is the dry IPN-membrane weight (g), and w0 is the unmodified-membrane

weight (g). This method quantitatively calculated the mass percent of the hydrophilic IPN.

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Fig. 1 Scheme of synthesis in situ of IPNs. a Isotactic PP first network, b PVA, c P(AA) network, d
P(SSNa) network, e P(ClVBTA) network, f P(GMA-NMG) network. The ultrafiltration cell was used to
carry out the impregnation of the reactive solution and the aluminum plates were the free polymerization
reaction

Water-uptake percentage The weight of the dry IPN-modified membrane samples

were measured before wetting with Type I distilled, deionized water for 24 h. All
tests occurred at room temperature. The weight of the modified membranes was
measured 3 times because the membranes are porous. The water excess was
removed from the modified wet membranes using an absorbent paper in all the tests.
During this period, the samples reached the swelling equilibrium. The water-uptake
percent (% Ww) was calculated from Eq. 2:


wwet  wdry
%Ww
 100 %;
2
wdry
where wwet is the wet IPN-membrane weight (g), and wdry is the dry IPN-membrane
weight (g). This method is gravimetric.
Volumetric flux The time required for 50 mL of the deionized water to pass
through a modified membrane was determined. A pressure of 1 bar was maintained
for all the tests. The equipment used during this step was a stirred-cell filtration unit
(Amicon) that works with nitrogen gas. This analysis probes the IPN formation in
the pores.

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Sorption of Cr(III) and Cr(VI) ions These experiments were performed by the
batch method to determine the capacity of the fixed functional groups toward
chromium ions. The size of the membrane samples were 1 cm2. Cr(III)-sorption
experiments were performed by P(SSNa), P(AMPS), P(AA), and P(AGA) IPN
membranes using a Cr(III) solution of 2.8 9 10-4 mol/L at pH 3.0. Cr(VI)-sorption
experiments were performed by P(ClVBTA), P(ClAETA), and P(GMA-NMG) IPN
membranes using a Cr(VI) solution of 2.8 9 10-4 mol/L at pH 3.0. All samples
were soaked in 10 mL of solution for 7 days. The quantities of Cr(III) and Cr(VI)
were determined using a UVVisible spectrophotometer. The concentration of the
Cr(III) and Cr(VI) ions adsorbed onto the IPN membranes was determined from
Eq. 3:


C0  Ceq;t
Qt
 V  1000;
3
Wdry
where C0 is the chromium ion concentration (mmol/L) at time zero, Ceq,t is the
chromium ion concentration (mmol/L) at infinite-time equilibrium, V is the volume
(L) of the system and Wdry is the dry IPN-membrane weight (g).
Electrokinetic properties Brookhaven ZetaPlus equipment was used. The membrane samples were cut into thin pieces and submerged into 5 9 10-2 mol/L KCl
solutions at pH values of 3.0, 7.0, and 9.0. The electrokinetic potential 1 was
determined from the ionic mobility (le) by using the Smoluchowski (Eq. 4):
le

e1
;
g

where le is the ionic electrophoretic mobility [(l/s)/(V/cm)], e is the liquid permittivity [J/(V2 9 m)], and 1 is the electrokinetic potential or the zeta potential
(mV). The pH was controlled using HCl and NaOH.
Morphological and microstructural characterization
Fourier transform-infrared (FT-IR) spectroscopy Using a Nicolet FT-IR instrument with a DTGS-KBr detector (Omnic 5.2 Nicolet Instrument Corp.), the FT-IR
spectra of the IPN-modified and unmodified membranes were obtained. The
measurement was collected between 400 and 5000 cm-1.
Scanning electron microscopy with X-ray microanalysis (SEM/EDS) A 20,000-kV
JEOL microscope (JSH 6380LV model) was used, and an Oxford Instruments
INCAX-sight was used for the Energy Dispersive X-ray Spectroscopy (EDS)
measurements. This technique was used to analyze the superficial morphology
changes in the modified and unmodified membranes.

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Polym. Bull.

Ion-transport of the Cr(III) and Cr(VI) ions

A dual-chamber diffusion cell (feed and receiver phases) was used to evaluate the
IPN transport membranes, and the functional membrane was placed between the
chambers. Figure 2 shows a transport cell working under the Donnan equilibrium
principle. Each chamber had a 250 mL capacity and was filled with 150 mL of the
working solution for the tests.
Experimental design Binary Cr(III)/Cr(VI) mixture solutions were prepared in the
feed chamber. The initial concentrations in the feed chamber are shown in Table 2.
In both chambers, the pH was 3.0 for all experiments. P(ClVBTA), P(ClAETA),
P(GMA-NMG), P(SSNa), P(AMPS), P(AA), and P(AGA) IPN membranes with 6
and 15 mol% of MBA were tested, along with MPVA and MPEI-grafted
membranes. Prior to the Donnan dialysis experiments, all membranes were
converted into the Cl- form (cationic, chelating membranes), or the Na? form
(anionic, chelating membranes). Every 60 min for 8 h, 3 mL was extracted from the

Fig. 2 Scheme of Donnan dialysis transport

Table 2 Experimental
conditions of the feed and
receiving chamber at pH 3.0

Binary system

Initial concentration (mol/L)

Feed solution
[Cr(III)]

123

Receiving chamber
[Cr(VI)]

[NaCl]
1.0

6.4 9 10-3

1.0 9 10-4

-3

8.0 9 10

2.5 9 10-4

8.0 9 10-3

5.0 9 10-4

Polym. Bull.

Fig. 3 Cr(III) and Cr(VI) ions wavelength absorption values. [Cr(III)] is 4 9 10-4 mol/L and [Cr(VI)] is
1 9 10-5 mol/L

receiving chamber. Direct UVVisible spectrophotometry was used to measure the

Cr(III) and Cr(VI) ion concentrations (see Fig. 3). The samples were returned to the
receiving chamber after measuring their chromium ion concentrations.
The transport of Cr(III) and Cr(VI) ions was evaluated based on the enrichment
factor (%Ef), calculated using Eq. 5:
!
e
Ve  Ci:t
%Ef 100 
;
5
f
Vf  Ci;0
where Ve and Vf (L) are the extraction chamber and feed chamber volumes,
e
respectively, and Ci;t
is the ion concentration in the extraction chamber, which
changes with time. Thus, Cfi,0 was the ionic concentration in the feed chamber at
time 0, and the ions present could be Cr(VI) or Cr(III). The results of modified IPNs
membranes were compared with those of hydrophilic, commercial PVDF membranes of type MGV and MHVLP, and also for the MplasmaCl and MplasmaNa.

Results and discussion

Synthesis and characterization of the functionalized microporous PP
membranes
The evaluation of the modified membranes must consider the changing on
modification percent, water-absorption capacity, and sorption toward specific ions.
These samples were compared with a unmodified microporous membranes. The

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Polym. Bull.

MP(AA)15 %, MP(AGA)6 %, and MP(AA)10 % membranes had increasing

percentage of modifications. The percentage of modification is a function of the
crosslinking reagent (MBA) concentration: if the concentration increases, then the
percent modification will be higher. The percentage of modification in all samples
gradually increased from 0 to 5.2 % (see Table 3). These results imply that the
porous MPP membranes are filled by crosslinked polyelectrolyte chains.
The percentage of modification values of the MP(AGA)6 % and MP(AGA)15 %
are very similar, the same case occurs for the MP(AMPS)6 %, MP(AMPS)15 %,
MP(ClAETA)6 %, and MP(ClAETA)15 %. The MBA mol% of the MP(AGA)6 %
and MP(AGA)15 % dont have effect in the growth control to the networks similar
to the MP(AA), MP(GMA-NMG), MP(ClVBTA), and MP(SSNa), the same case
occur to the MP(AMPS)6 %, MP(AMPS)15 %, MP(ClAETA)6 %, and
MP(ClAETA)15 %.
It is possible that the free radical polymerization of the monomers (AGA, AMPS,
and ClAETA) was faster than the monomers (ClVBTA and SSNa) due to these
monomers are highly hydrophilic, and they are more soluble in the reaction media.
This is the reason to do not make the change of the membranes (MP(AGA),
MP(AMPS), and MP(ClAETA)) using 10 mol% of the MBA. In this research, the
monomers (AA and GMA-NMG) are considered as the basis for making membranes
with chelating properties of chromium ions, hence the concentration of MBA
completely changed.
Table 3 Optimum values of modified degree percentage, water uptake percentage, volumetric flux and
sorption towards the Cr(III) or Cr(VI) ions
Code sample

%PM

%Ww

Qt (mmol/g)

Volumetric flux (L/m2 h)

MP(AA)6 %

2.1

21.2

71.9

58.9

MP(AA)10 %

4.1

19.2

67.4

49.2

MP(AA)15 %

5.2

16.5

54.9

28.3

MP(SSNa)6 %

1.9

38.2

164.8

64.6

MP(SSNa)10 %

3.7

31.5

117.7

50.5

MP(SSNa)15 %

4.4

29.7

95.8

23.3

MP(AGA)6 %

4.5

14.8

49.8

41.0

MP(AGA)15 %

5.1

11.3

32.5

26.2

MP(AMPS)6 %

3.9

24.4

90.4

44.6

MP(AMPS)15 %

4.2

20.9

67.2

27.9

MP(ClVBTA)6 %

3.6

36.3

203.0

48.5

MP(ClVBTA)10 %

3.7

33.9

137.3

49.8

MP(ClVBTA)15 %

4.5

27.9

98.9

24.6

MP(GMA-NMG)6 %

0.9

18.7

156.5

74.7

MP(GMA-NMG)10 %

1.1

17.2

98.8

65.8

MP(GMA-NMG)15 %

1.9

15.9

74.7

40.7

MP(ClAETA)6 %

1.6

33.2

154.5

64.4

MP(ClAETA)15 %

2.1

22.1

65.7

38.5

MPP

90.3

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Polym. Bull.

The percentage of water uptake and change in the volumetric flux of water
decreased for all membrane samples because the pore size decreased, which
produced resistance to the water. These results by the modified membranes were
low relative to the MPP sample (see Table 3). As the MBA crosslinking reagent
increased, the water uptake and hydrophilicity of the membranes decreased due to
the compact structure of the IPNs. Although MBA provides a rigid structure for the
membrane, it also contributes to the brittleness of these. However, a high degree of
crosslinking is favorable for the stability of membranes. The percent water uptake
results of the MP(SSNa)6 %, MP(ClVBTA)10 %, and MP(SSNa)15 % are more
high in comparison than, the MP(AGA)6 %, MP(GMA-NMG)10 %, and
MP(AGA)15 %. On the other hand, MP(AGA)6 %, MP(AA)10 %, and
MP(SSNa)15 % are less than the results of the volumetric flux of water (see
Table 3). These differing results occurred because of the morphology in the layer
shape and the agglomerated, amorphous particles.
The values for the sorption of Cr(III) or Cr(VI) ions by the fixed functional
groups indicate the quantity of ion-exchangeable sites in each membrane. This
specific capacity of the modified membrane depends on the percentage of water
uptake. If the degree of crosslinking increases, then percent water uptake decreases,
which results in less sorption of the Cr(III) or Cr(VI) ions by the IPN membranes
(see Table 3). The expansion of IPNs was successfully suppressed with the help of
the MPP porous support. The fixed functional groups require water molecules to
transfer ions through the membrane, which determines the specific selectivity.
The sorption towards Cr(VI) ions using the cationic and chelating membranes
follow the decreasing order from higher to lower value: MP(ClVBTA)6
% [ MP(GMANMG)6 % [ MP(ClAETA)6 % [ MP(ClVBTA)10 % [ MP(ClV
BTA)15 % [ MP(GMA-NMG)10 % [ MP(GMNMG)15 % [ MP(ClAETA)15 %
(see Table 3). While, the decreasing order on the sorption of Cr(III) ions using the
anionic and chelating membranes is: MP(SSNa)6 % [ MP(SSNa)10 % [ MP(SSNa)15 % [ MP(AMPS)6 % [ MP(AA)6 % [ MP(AA)10 % [ MP(AMPS)15 %
[ MP(AA)15 % [ MP(AGA)6 % [ MP(AGA)15 % (see Table 3).
The result means that the functional groups of the membranes have less free
space when was increasing of the MBA concentration, and they are more isolated
and not available for ion exchange.
The MPVA and MPEI membranes produced the following results: percent
modification of 4.5 9 10-1 %, water uptake percentage of 10.1 %, volumetric flux
change of 88.4 L/m2 h, and sorption toward Cr(III) ions of 15.5 mmol/L by MPVA;
and percent of modification of 3.2 9 10-1 %, water uptake percentage of 12.5 %,
volumetric flux change of 88.3 L/m2 h, and sorption toward Cr(VI) ions of
17.1 mmol/L by MPEI.
PVA and PEI grafted onto the MPP surface are important: these polyelectrolytes
form a hydrophilic layer and improve the wetting of the reactive monomers. PVA
and PEI are inexpensive polymers, and they have good flexibility, high chemical
resistance and good attachment onto various surfaces. Often, pore-filled membranes
fabricated on a reinforcing support material show good dimensional and chemical
stability over time.

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Polym. Bull.

Electrokinetic properties
The surface-charge distributions of the ion-exchange IPN membranes were
subjected to electrokinetic potential measurements, and the relative charge
characteristics and density of the charged surface were determined. The ionic
functional groups of the modified membranes cause superficial charges. The
electrokinetic potential is the fixed charge potential difference (cationic, anionic,
weak acid, and chelating groups) between the mobile ionic charges in the absorption
layer. The membrane stability, polyvalent ion absorption capacity and size can be
evaluated using the electrokinetic potential. The electrokinetic potential of each
membrane is mainly attributed to the ion-absorption capacity and the mobility of
ions within the membrane matrix. The surface charge is related to phenomena such
as wetting, adsorption, and ion transport.
The anionic and cationic functional groups in P(SSNa) and P(ClVBTA),
respectively were electrically charged across the entire pH range, as shown by
Eqs. 6 and 7.


R  SO
3 Na H2 O  R  SO3 H Na OH ;

R  N CH3 3 Cl H2 O  R  N CH3 3 OH H Cl :

The weakly acidic functional groups in the P(AA) at pKa4.8, and the chelating
group PVA at pKa 10.67 have dissociation constants dependent on the pH, P(GMANMG) at pKa6.19 and PEI at pKa10.6 with a fixed chelating group require a specific
pH for protonation of the nitrogen [22].
The dissociation of surface weak acid (P(AA) and PVA) or basic (P(GMA-NMG)
and PEI) functional groups, which belong to a class of Brnsted acids and bases, are
probably the main source of surface charges, as shown by Eqs. 8 to 11:
R  COOH H2 O  H3 O R  COO ;

R  OH H2 O  H3 O R  O ;

R  NH  C7 H16 O5 H2 O  OH R  NH  C7 H16 O5 ;

10

R  NH  R H2 O  OH R  NH  R:

11

The MPP membrane is hydrophobic without any modification and has no ionic
functional groups, which renders the membrane inert to electrical fields.
Figure 4 shows the behavior of the electrokinetic potential. The electrokinetic
potential depends on the IPN concentration, pH, and the capacity the electric double
layer formed. The P(ClVBTA) IPN membrane and PEI membrane exhibited higher
electrokinetic potentials when the pH was 3.0. These results depend on the basic
character of the functionalized surface and the excess H? repelling the quaternary
ammonium groups. The movement of the Cl- counterion in the diffusion layer
becomes favored when the pH is 3.0. At pH of 9.0, the electrokinetic potential
decreases due to the presence of OH- ions. These OH- ions compete with the Clions in the diffusion layer. P(GMA-NMG) IPNs at low pH values have a positively

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Polym. Bull.

50
40
30

(mV)

20
a
b
c
d
e
f

10
0
-10
-20
-30
2

10

pH
Fig. 4 Electrokinetic potential of modified membranes with IPNs with 5 9 10-2 mol/L of KCl.
a MP(AA)10 %, b MP(SSNa)10 %, c MP(ClVBTA)10 %, d MP(GMA-NMG)10 %, e MPVA, f MPEI

charged structure but, at high pH values, these are uncharged. PEI grafted into MPP
membranes exhibits the same behavior as for the P(GMA-NMG) IPNs.
The P(SSNa) and P(AA) IPN membranes and PVA membranes exhibited the
most negative electrokinetic potential values when the pH was 9.0. These results
depend on the acid character of the functionalized surface, and the excess OH- ions
repelled the groups fixed in the network and favored the movement of the Na?
counterion in the diffusion layer. When the pH was 3.0, the electrokinetic potential
became less negative because H? ions competed with the Na? ions in the diffusion
layer. P(AA) IPNs at low pH values have an uncharged structure, but at high pH
values, the carboxylic side groups are negatively charged, and because of the
electrostatic repulsion between the side groups, their conformation is that of an
extended structure. PVA grafted into MPP membranes has the same behavior as the
P(AA) IPNs. All of the results depend on the polyelectrolyte IPN concentrations.
Morphological and microstructural characterization
FT-IR analysis
In the microstructural analysis of the modified MPP membranes, the FT-IR
absorption bands corresponding to the functional groups were determined.
Figures 5a and 6a show the FT-IR spectrum for MPP (in cm-1). The unmodified
MPP membrane had characteristic absorption bands at 29702800 cm-1 corresponding to the stress and asymmetric stretching of CH (das) bonds in the (CH3)
methyl groups. The peak at 14801380 cm-1 results from the CH (das) of the CH2
bond flexion vibrations because these bonds have asymmetric deformations. The
symmetric interaction flexion vibrations for the CH (ds) in the CH3 bonds were
generated across the same range. The signals from 1300 to 700 cm-1 represent the
changing isotactic polypropylene microstructural characteristics. The signals at
1200, 1116, 998, 841, and 800 cm-1 are the isotactic configuration crystallinity

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Polym. Bull.

d
(R

% Transmittance

3 3

b
-(R-N+ (CH3)3)

a
-(CH3)

CH3

4000

3500

3000

2500

2000

1500

1000

Wavenumbers (cm -1)

Fig. 5 FT-IR spectra of: a MPP, b MP(ClVBTA)15 %, c MP(GMA-NMG)15 %, and d MP(ClAETA)15 %

e
(N H)

% Transmittance

d
2

(N H)

c
2

a
CH3

CH3

4000

3500

3000

2500

2000

1500

1000

Wavenumbers (cm-1)
Fig. 6 FT-IR spectra of: a MPP, b MP(AA)15 %, c MP(SSNa)15 %, d MP(AMPS)15 %, e MP(AGA)15 %

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Polym. Bull.

sequences [25]. The signal at 970 cm-1 corresponds to the monomeric head-to-tail
isotactic polypropylene configuration. The CH and CC bonds were observed in
the spectra for the modified and unmodified MPP membranes. These signals are
stronger in the modified membrane than in the unmodified MPP membrane. The
absorption signals (mas (CH2), das (CH2) and ds (CH2)) were stronger in the
modified membrane samples than in the unmodified MPP membrane signals.
Figure 5b shows the signals representing the P(ClVBTA) IPN membranes. The
aromatic (C=C) absorption signals occur in the range from 1400 to 1600 cm-1. The
quaternary ammonium group has absorption signals at 1581 cm-1 for the (NH)
bond and (CN) vibration and at 1483 cm-1 for the (N?(CH3)) group bond
flexion.
Figure 5c shows the characteristic absorption signals for the P(GMA-NMG) IPN
membranes. For the NMG portion, the vibrational bands included overlapping bands
at 1077 cm-1 (CO), 1035 cm-1 (CN) and one at 1174 cm-1 (CHOH). For the
GMA portion, the vibrational bands included 1719 cm-1 (C=O) and 1563 cm-1
(COO) [22].
Figure 5d shows stretching signals at approximately 3430 cm-1 (NH),
3000 cm-1 (CH), and 1732 cm-1 (C=O ester bond), and at 1483 cm-1 for the
(N?(CH3)) group bond flexion to the P(ClAETA) IPN membranes. Table 4 shows
the characteristic absorption signal values of the quaternary ammonium and Nmethyl-D-glucamine functional groups.
Figure 6b shows the characteristic absorption signals for the P(AA) IPN
membranes. The characteristic absorption band at 1690 cm-1 is due to the presence
Table 4 Characteristic absorption signals (cm-1) of the samples of interpenetrating polymer networks
membranes with quaternary ammonium and N-methyl-D-glucamine groups
Functional group
signal/sample

MPP

MP(ClVBTA)15 %

MP(ClAETA)15 %

MP(GMANMG)15 %

m(NH) o

36003200

36003200

m(OH)
mas(CH)

29702800

m(CH)

30252928

3020

m(C=O)

1732

1719

m(CHOH)

1174

m(CO)

1077

m(C=C)

16411408

m(CN)

1035

d(NH)

1581

1581

d(NH) de

1417

1483

Aromatic ring

RN?(CH3)3
das(CH)

14801380

ds(CH)

916716

Crystallinity

1300700

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Polym. Bull.
Table 5 Characteristic absorption signals (cm-1) of the samples of interpenetrating polymer networks
membranes with the sulfonic acid and carboxylic acid
Functional group
signal/sample

MP(SSNa)15 %

MP(AMPS)15 %

MP(AA)15 %

MP(AGA)15 %

m(NH) o

36003200

36003200

36003200

36003200

m(OH)
mas(CH)

30502900

30502900

30502900

30502900

m(CH)

m(C=O)

1644

17251700

17251700

m(CHOH)

m(CO)

masym(COO-)

1640

1640

m(C=C)

16411408

m(CN)

1453

1453

masym(SO2)

12561217

1115

msym(SO2)

10611020

1047

d(CH)

916716

d(NH)

1552

Aromatic ring

of a (C=O) stretching vibration, and the band at 3400 cm-1 is due to the (OH)
stretching vibration. The absorption band at approximately 2930 cm-1 is due to C
H stretching polymer backbone, and the (CO) stretching absorbed at 1150 cm-1.
Figure 6c shows the characteristic absorption signals for the P(SSNa) IPN
membranes. The SO3- from the sulfonate group was observed at 1042 cm-1 (S=O)
and 1175 cm-1, and the band at 14001600 cm-1 corresponded to the aromatic
(C=C) carbons.
Figure 6d shows the characteristic absorption signals for the P(AMPS) IPN
membranes. The band at 1644 cm-1 is due to the stretching vibration of (C=O)
double bond and that at 1453 cm-1 is the vibration of (CN). The bands at 1115 and
1047 cm-1 are due to the asymmetric and symmetric vibration of (S=O),
respectively, which were the characteristic absorption of P(AMPS).
Figure 6e shows the characteristic absorption signals for the P(AGA) IPN
membranes. The band at 3416 cm-1 is due to the stretching (NH) of amide groups
and (OH). The bands at 1540 and 1671 cm-1 are due to the asymmetric stretching
of the (CO) of the carboxylate anion.
Table 5 shows the characteristic absorption signal values of the sulfonic acid and
carboxylic acid functional groups.
SEM analysis
The morphological changes were observed using SEM. The membrane morphology
changes for the IPN membranes were compared with those changes for the
unmodified MPP membrane. These results represent an anisotropic membrane.

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Polym. Bull.

Figure 7a, b shows the morphology of a unmodified microporous MPP

membrane. The membrane face (see Fig. 7a) had an intertwined fiber structure,
low porosity, and smooth superficial aspect. In Fig. 7b a high density was observed
based on the thick, compacted fiber group.
Figure 7c, d shows the MP(AA)15 % membrane morphology. The membrane
exhibited two phases relative to the unmodified MPP membrane, and also the
MP(AMPS)15 % (see Fig. 7e, f), the MP(SSNa)15 % (see Fig. 7g, h) and the
MP(AGA)15 % (see Fig. 8a, b) displayed the same structure such as the
MP(AMPS)15 %. The P(SSNa) IPN particle sizes were larger and more agglomerated than the P(AA), P(AMPS), and P(AGA) IPNs. The particle IPNs covered the
entire polypropylene fiber surface like a layer. An EDS elemental analysis on the
cross-sectional area of the MP(AA)15 % (see Fig. 7d) detected oxygen belonging to
the carboxylic group and carbon belonging to the structure of the polymer.

Fig. 7 SEM/EDS images of the modified MPP microporous membranes cross-section area, and
unmodified membranes to 10 lm and 9 1000. Unmodified MPP membrane (a surface of membrane,
b EDS of the cross-section area). MP(AA1)5 % membrane (c surface of membrane, d EDS of the crosssection area). MP(AMPS)15 % membrane (e surface of membrane, f EDS of the cross-section area).
MP(SSNa)15 % membrane (g Surface of membrane, h EDS of the cross-section area)

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Polym. Bull.

Fig. 8 SEM/EDS images of the modified MPP microporous membranes cross-section area, and
unmodified membranes to 10 lm and 9 1000. MAGA15 % membrane (a surface of membrane, b EDS
of the cross-section area). MP(ClVBTA)15 % membrane (c surface of membrane, d EDS of the crosssection area). MP(ClAETA)15 % membrane (e surface of membrane, f EDS of the cross-section area).
MP(GMA-NMG)15 % membrane (g surface of membrane, h EDS of the cross-section area)

Similarly, an EDS spectrum was obtained for the MP(AGA)15 % (see Fig. 8b)
with similar results as for MP(AA)15 %. On the other hand, the EDS analysis on the
cross-sectional area of the MP(AMPS)15 % (see Fig. 7f) and MP(SSNa)15 % (see
Fig. 7h) membranes detected the sodium and sulfur of the sulfonate group. The
P(AA), P(AMPS), and P(AGA) IPNs were better distributed relative to the P(SSNa)
IPN, and they tended to be more homogeneous and cover more polypropylene fibers

123

Polym. Bull.

than the P(SSNa) IPNs. The P(AA) and P(AGA) IPNs were smaller than the
P(SSNa) and P(AMPS) IPNs.
Figure 8c, d shows a SEM image of the MP(ClVBTA)15 % membrane with IPN.
These membranes also exhibited two phases in contrast to the unmodified MPP
membrane, and also the MP(ClAETA)15 % (see Fig. 8e, f) and the MP(GMANMG)15 % (see Fig. 8g, h) displayed the same structure such for
MP(ClVBTA)15 %. However, MP(GMA-NMG)15 % displays a structure more
similar to that of MP(SSNa)15 %. These results indicate a change in the
microstructural homogeneity compared with that of the unmodified MPP membrane
(see Fig. 8g).
The P(ClVBTA) and P(ClAETA) IPNs covered the entire polypropylene fiber
surface like a paint. EDS elemental analysis was obtained from the cross-sectional
area and measured the elemental concentration for the Cl- counterion of
MP(ClVBTA)15 % and MP(ClAETA)15 %. This indirect method probed the
quaternary ammonium group in the IPNs. The highest P(GMA-NMG) IPN
concentration was found on the superficial face relative to the observed membrane
cross-section.
Previous research showed similar results using SEM. For example, MPP
membranes had poly(vinylbenzyl ammonium salts) crosslinked in situ within its
pores [26]. Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) was grafted
and crosslinked onto the PP membrane surface. The membrane had an 80 %
porosity with a 0.20-lm pore size [27]. Similar results were obtained when a
polypropylene film was superficially modified with P(SSNa) and a polyethylene film
was modified with P(SSNa). The main results found a structural surface change
where small particles with small pores appeared [28].
The cationic and weak acid polyelectrolyte IPNs went deeper into the MPP
membrane structure than the cationic and chelating IPNs. The P(GMA-NMG), and
P(SSNa) IPNs agglomerated in large quantities on the surface, which makes
accessing the ion-exchange groups easier. In general, the membranes exhibited low
IPN concentrations in their cross-sections due to the hydrophobic nature of the
isotactic polypropylene and low pore uniformity due to their highly asymmetric
character.
Transport evaluation of Cr(III) and Cr(VI) from mixed system
The transport capacity for a mixture of Cr(III)/Cr(VI) ions through modified MPP
membranes was evaluated. The Cr(VI) and Cr(III) concentrations are suitable for
interacting with the fixed charges in the membrane.
Under these experimental conditions (pH of 3.0, strongly stirred, and room
temperature), Cr(VI) exists mainly in the form of HCrO4- at (1.0 9 10-4,
2.5 9 10-4, and 5.0 9 10-4 mol/L), and Cr(III) can exist in the forms CrOH2? and
-3
Cr(OH)?
and 8.0 9 10-3 mol/L) [29]. Figure 9 shows the
2 at (6.4 9 10
enrichment-factor profile for a binary compound solution mixture containing
Cr(III) and Cr(VI) ions. The extraction reagent was 1 mol/L NaCl. Table 6 displays
the enrichment-factor values of the various binary solution mixtures using modified,
plasma, polyelectrolyte grafted, and hydrophilic commercial membranes.

123

Polym. Bull.

70

70

60

60
MP(ClVBTA)6%
MP(ClVBTA)15%
MP(GMA-NMG)6%
MP(GMA-NMG)15%
MPEI
MPP

% (Ef)

40
30

50
40
% (E f )

50

30

20

20

10

10

0
0

150

300

MP(ClVBTA)6%
MP(ClVBTA)15%
MP(GMA-NMG)6%
MP(GMA-NMG)15%
MPEI
MPP

450

150

Time (Minute)

c 70

450

70

60

60

50

50

40

40

30

MP(SSNa)6%
MP(SSNa)15%
MP(AA)6%
MP(AA)15%
MPVA
MPP

20
10
0

% (Ef)

% (Ef)

300
Time (Minute)

MP(SSNa)6%
MP(SSNa)15%
MP(AA)6%
MP(AA)15%
MPVA
MPP

30
20
10
0

150

300
Time (Minute)

450

150

300

450

Time (Minute)

Fig. 9 Enrichment factor profile of Cr(III) and Cr(VI) ions at pH 3.0. a Cr(III) profile to system 1,
b Cr(VI) profile to system 1, c Cr(III) profile to system 3, d Cr(VI) profile to system 3

The Donnan equilibrium for the Cr(III) ions of system 1 (see Table 2) was
achieved between 240 and 300 min (see Fig. 9a), and the Donnan equilibrium for
the Cr(VI) ions of system 1 was reached between 240 and 300 min (see Fig. 9b).
While, the Donnan equilibrium for the Cr(III) ions of system 3 (see Table 2) was
achieved between 300 and 360 min (see Fig. 9c), and the Donnan equilibrium for
the Cr(VI) ions of system 3 was achieved between 300 and 360 min (see Fig. 9d).
However, the Donnan equilibrium for the Cr(III)/Cr(VI) ions using MPP (see
Fig. 9) was reached between 180 min, and for MPEI (see Fig. 9a and b) and MPVA
(see Fig. 9c and d), the Donnan equilibrium was achieved between 180 and
240 min, respectively. These results depend on the chromium concentrations,
functional group, and degree of crosslinking in the membranes. The Cr(III) and
Cr(VI) ionic fluxes depend of the morphological change of the modified membranes
with respect to that of MPP. Quaternary ammonium functional IPN membranes
(MP(ClVBTA)6 %,
MP(ClVBTA)15 %,
MP(ClAETA)6 %,
and
MP(ClAETA)15 %) produced Cr(VI) ion-selective separation of the feed mixture.
The % Ef (Cr(VI)) obtained by these membranes is between 30 to 60 %.
The quaternary ammonium membranes demonstrate high performance by the
Cr(VI) ion with binary solution mixture 1 (see Fig. 9b; Table 6). Low Cr(III) and
Cr(VI) concentrations in the feed phase aided the pre-concentration process of
Cr(VI) in the receiving chamber. MP(ClVBTA)6 % achieved good results. The low

123

Polym. Bull.
Table 6 Values of enrichment factor (%Ef) in the receiving chamber in a binary system
Membrane code

%Ef 1 9 10-4
1

Cr(III)

Cr(VI)

Cr(III)

MP(ClVBTA)6 %

5.8

61.2

8.9

43.5

9.9

MP(ClVBTA)15 %

3.8

53.3

2.4

43.2

2.1

30.6

MP(ClAETA)6 %

9.1

47.9

9.6

40.9

10.8

42.9

2.5

37.9

2.3

40.9

5.4

39.1

55.2

57.6

48.4

30.6

48.6

17.2

MP(ClAETA)15 %
MP(GMA-NMG)6 %

Cr(VI)

Cr(III)

Cr(VI)
55.9

MP(GMA-NMG)15 %

54.8

45.3

48.5

38.9

51.2

21.9

MP(AA)6 %

59.1

22.8

46.5

15.4

42.5

9.7

MP(AA)15 %

22.4

21.8

39.9

15.9

36.3

9.4

MP(AGA)6 %

43.8

13.3

46.1

10.7

45.3

6.7

MP(AGA)15 %

30.8

4.5

35.3

5.3

21.9

3.5

MP(SSNa)6 %

51.6

4.7

46.0

4.0

42.1

2.5

MP(SSNa)15 %

33.2

3.6

38.6

2.5

25.3

1.5

MP(AMPS)6 %

63.4

10.9

55.6

8.1

50.3

4.9

MP(AMPS)15 %

54.5

4.9

47.2

7.6

46.6

4.7

MPVA

12.4

10.2

6.1

5.3

10.4

2.9

MPEI

19.5

32.3

14.9

30.1

14.6

21.8

MplasmaCl

6.2

48.1

16.9

43.9

26.0

51.1

MplasmaNa

52.9

4,6

40.8

9.9

37.1

6.9

MGV

57.3

59.9

61.2

62.3

80.5

80.3

MHVLP

64.4

63.7

64.6

64.1

56.8

56.1

2.3

2.6

2.6

3.1

2.4

1.6

MPP

values of % Ef (Cr(III)) using these membranes were due to Donnan exclusion

principle. This principle is produced because of the electrostatic repulsion of the
positive group fixed and the Cr(III) ions. MplasmaCl demonstrates good separation
of Cr(VI) of the Cr(III) feed mixture phase in all binary solution mixtures. For
system 1, the MplasmaCl produced a high % Ef value of Cr(VI) ion. The
MplasmaCl has similar results for the separation of Cr(VI) ions, such as the
quaternary ammonium IPN membranes (P(ClVBTA) and P(ClAETA)) and the
exclusion of Cr(III) ions.
Carboxylate IPN membranes (P(AA) and P(AGA)) present a good selectivity
toward the Cr(III) ions of the feed phase. These membranes did not have their ionic
fixed functional groups completely dissociated, as the pH value was 3.0. At pH 3.0,
it was demonstrated that the superficial electric charge of potential electrokinetic is
close to zero. Even so, the % Ef of Cr(III) was until 60 %, by the MP(AA)6 %, and
MP(AGA)6 % (see Fig. 8c; Table 6). Moreover, the MP(AA)15 %, and
MP(AGA)15 %, the % Ef was until 36 % of Cr(III). On the other hand, the % Ef
of Cr(VI) was lowest, when the crosslinking degree of the membranes increased.

123

Polym. Bull.

These results of Cr(VI) are a function of the Donnan exclusion principle. The
MP(AA)6 % developed the highest separation of Cr(III) of feed phase with 42.5 %
by Cr(III), and 9.67 % by Cr(VI), and the MP(AGA)6 % with 45.3 % by Cr(III),
and 6.69 % by Cr(VI) ions.
Furthermore, this transport process using the carboxylate membranes is balanced
by the pumping of Na? and H? ions that move in the counter balance. Additionally,
in these experiments, the important role of the charge on the membrane was checked
because of the charge aids in the mobility of ions [30].
Sulfonate IPN membranes demonstrate more high selectivity towards the Cr(III)
ions than the carboxylate IPN membranes. These membranes provide a good barrier
to limit Cr(III) transport. The conditions of binary solution mixture 3 produced a
high efficient in the ion separation of the feed mixture. The high values of % Ef
(Cr(III)) were 42.1 % for the MP(SSNa)6 % (see Fig. 9c, a) and 50.2 % for the
MP(AMPS)6 %. In contrast, the %Ef values of Cr(VI) were less than the values for
the other binary solution mixtures and the carboxylate IPN membranes.
The Donnan exclusion principle was the main reason for the selective transport
of the Cr(III) ions (see Fig. 9c, d; Table 6). MplasmaNa demonstrated great
performance in the binary solution mixture 1. P(SSNa) and P(AMPS) IPN
membranes showed similar results of selective separation of Cr(III) ions from the
feed phase compared with the results of the MplasmaNa and with the Cr(VI)
electrical exclusion of membranes.
NMG IPN membranes show very similar values of the Cr(III) and Cr(VI)
transport (see Fig. 9a; Table 6). At pH 3.0, the NMG group has a positive charge
and is located in the nitrogen. The positive charge allows the Cr(III) transport
towards the receiving chamber. The Cr(VI) ions react with the hydroxyl groups of
the NMG and they were reduced to Cr(III) [30].
Probably, the concentration gradient between the feed phase and the receiving
phase aided the separation of Cr(III) bound to the hydroxyl groups. Surely, this is
the main reason for the high Cr(III) concentration in the receiving chamber. Binary
solution mixture 3 shows a high Cr(III) concentration in the receiving chamber.
MP(GMA-NMG)6 % and MP(GMA-NMG)15 % do not show different results in
the selective transport.
A high selective separation of Cr(VI) from the feed phase using the (P(ClVBTA),
and P(ClAETA)) anion IPN membranes was expected, and in the same way, a high
elective separation of Cr(III) from the feed phase mixture employing (P(SSNa), and
P(AMPS)) cation IPN membranes was expected. Because these membranes have a
strong ion fixed group, they can make an exchange reaction with the chromium
species.
Nevertheless, the sorption of chromium species Na?, Cl-, and H? suggests that
some amount of these species can pass to the opposite side without the
stoichiometry predicted by the ion-exchange reaction. The same behavior was
observed with the carboxylate IPN membranes, although these membranes had a
low negative charge on the surface. Additionally, this explanation can complete the
reason of the behavior of P(GMA-NMG) membranes with high transport of Cr(III)
ions.

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Polym. Bull.

MPVA and MPEI show low results of the %Ef to separated Cr(III) of Cr(VI).
However, these results are good response of this method to modify the surface of
MPP membranes. Nevertheless, it is possible to observe a selectivity in the selective
transport of Cr(III) or Cr(VI) (see Table 6; Fig. 9).
MPVA aided the Cr(III) transport, and MPEI aided the Cr(VI) transport.
Regardless of the small amount of PVA and PEI concentration inside of pores, it
was demonstrated that the driving force for Donnan dialysis is the high
concentration of NaCl reagent in the receiving phase that leads to the effective
pumping of ions.
MPP has the lowest results of the selective separation by the speciation of Cr(III)/
Cr(VI) mixture (see Table 6). These results are produced because of the high
hydrophobic character of the polypropylene fibers. This behavior can prohibit the
transport of chromium ions toward the receiving chamber. Hydrophilic commercial
membranes (MGv and MHVLP) showed high % Ef values of Cr(III) and Cr(VI)
transport, but these did not develop selective ion exchange properties to separate the
Cr(III)/Cr(VI) ion mixture (see Table 6).
The modified IPN membranes have higher selective ion exchange properties than
the commercial membranes to separate speciation of trace metals ions in aqueous
systems.

Conclusions
Microporous MPP with ion exchange capacities can be obtained by synthesizing
IPNs using radical polymerization. The functional monomer and crosslinked MBA
concentrations play important roles in IPN membranes synthesized in situ
because they can control the network density.
The hydrophilicity of P(ClVBTA), P(GMA-NMG), P(ClAETA), P(AGA),
P(AA), P(AMPS), and P(SSNa) IPNs were evaluated via SEM/EDS, FT-IR, and
electrokinetic studies. These results demonstrated the IPNs form within the pores.
IPNs effectively improve the hydrophilicity of MPP membranes according to results
of the percent modification, water uptake percentage, and volumetric flow change.
These values show a downtrend with an increasing amount of MBA crosslinking
agent because the IPNs are more compact at higher crosslinking degree.
The selective transport properties for the separation of the Cr(III) and Cr(VI) ions
mixture were evaluated using the Donnan dialysis principle. The Cr(III) ions was
selectively separated using MP(SSNa)6 % (42.12 %) respect to (2.53 %) by the
Cr(VI) ions in the binary mixture solution 3. The Cr(VI) ions was selectively
separated using MP(ClVBTA)6 % (61.22 %) respect to (5.78 %) by the Cr(III) ions
in the binary mixture solution 1. These results were influenced by various factors
including the hydrated radius of ion metals, superficial charges, solution concentration of the feed phase, and steric effects. Also, the MPP support and IPNs
structure enhanced the swelling and collapse of the network membranes, and the
Donnan exclusion principle and equilibrium, were influenced of the ion transport.
The MPP modified with IPNs were valued in terms of their selective transport
capacity, simplicity, and synthesis time. These modified membranes show good

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Polym. Bull.

stability and can be used in the softening of water process. The Cr(VI) and Cr(III)
extraction results were also important because the starting material was initially
hydrophobic, and the wetting properties improved upon modification.
Acknowledgments The authors thank the FONDECYT (Project No. 1150510), PIA (Anillo ACT-130),
REDOC (MINEDUC Project UCO1202 at U. de Concepcion), Marie Curie Program Actions Grant 7FPMC, CHILTURPOL2 (PIRSES-GA-2009 Project, Grant No. 269153). Julio Sanchez thanks FONDECYT
(Project No. 11140324), and CIPA, Chile.

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