Article

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Ion-Stabilized Membranes for Demanding Environments Fabricated

from Polybenzimidazole and Its Blends with Polymers of Intrinsic
Microporosity
Gergo Ignacz,† Fan Fei,‡,§ and Gyorgy Szekely*,†
†
School of Chemical Engineering and Analytical Science, University of Manchester, The Mill, Sackville Street, Manchester M1 3BB,
United Kingdom
‡
School of Materials, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom
§
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Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, United Kingdom
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*
S Supporting Information

ABSTRACT: Robust, ion-stabilized membranes from poly-

benzimidazole (PBI) and its blends with polymer of intrinsic
microporosity (PIM-1) were fabricated for organic solvent
nanofiltration in polar aprotic solvents (PAS). Flat sheet
membranes comprised of polybenzimidazole and 4−12 wt %
PIM-1 were fabricated via conventional phase inversion followed
by the reduction of nitrile PIM-1 to amine PIM-1. Stabilization
of the membranes was achieved via ion formation (chloride salt)
under acidic conditions. Such simple ion-stabilization method-
ology could replace cumbersome cross-linking. The aging of the
membranes and the their performance at room and elevated
temperatures, in a wide range of pH, in the presence of organic
bases, in six conventional and two green PAS, were investigated.
The PIM-1 content enabled fine-tuning of the molecular weight cutoff (MWCO) of the membranes between 190 and 650 g
mol−1.
KEYWORDS: polymer of intrinsic microporosity, organic solvent nanofiltration, polar aprotic solvent, temperature effect,
ion stabilization

■ INTRODUCTION
Organic solvent nanofiltration (OSN) is a promising
sustainable technology for molecular level separations.1 One
of the key challenges in membrane-based separations is the
stability of polymers in harsh organic solvents, in particular
polar aprotic solvents (PAS).2 Despite their drawbacks such as
toxicity and high boiling point, they are widely used in the
chemical industries due to their excellent solubility properties
in the SN2 type reactions, coupling reactions, and amide
formations. They are also often used for the dissolution of
active pharmaceutical ingredients (API) due to their mid-range
lipophilicity, i.e., having both acidic and basic moieties. Green
alternatives such as 2-methyltetrahydrofuran (MeTHF) and
propylene carbonate (PC) to substitute the undesired
conventional PASs are emerging in the literature;3 however,
their industrial viability is yet to be demonstrated. Con-
sequently, it is necessary to develop membranes that are stable
in PAS, which could facilitate the implementation of OSN by
the industrial sector.
Chemical cross-linking aims to increase the stability of
polymer membranes under harsh environments such as PAS.
However, most of these methods employ toxic substances such
as aliphatic diols,4 aliphatic and aromatic diamines,2,5,6 and
halogenated,13 epoxy,7 or heteroaromatic8 cross-linkers, often
at elevated temperature. Moreover, the cross-linking process
can significantly compromise the permeance of the mem-
branes.9,10 Polybenzimidazole (PBI) membranes for OSN are
emerging in the literature, which have been successfully used
for various applications.11,12 Livingston et al. developed the
first stable PBI membranes using a dibenzyl cross-linker at
elevated temperature,10,13 while Chung et al. focused on more
sustainable approaches via reducing the cross-linking temper-
ature and employing green solvents.9,14 This work aims to
explore ion stabilization via salt formation of the amine groups
of the benzimidazole moiety, which eliminates the need for the
undesired chemical cross-linking (Figure 1).
Lively et al. have recently critically assessed the potential of
microporous materials for OSN.15 Microporous membranes
comprising conjugated polymers on polyacrylonitrile (PAN)
with rigid backbones with ultrafast permeation were recently
reported.16 Polymers of intrinsic microporosity (PIM) were
used to fabricate thin film composite OSN membranes on
Received: September 7, 2018
Accepted: October 22, 2018
Published: October 22, 2018

© 2018 American Chemical Society 6349 DOI: 10.1021/acsanm.8b01563

ACS Appl. Nano Mater. 2018, 1, 6349−6356
ACS Applied Nano Materials Article

Figure 1. Schematic overview of the fabrication methodology for PBI and amine PIM-1 polymer blend membranes: (a) casting of a dope solution
comprised of PBI and PIM-1; (B) phase inversion in water followed by BH3·SMe2 treatment to reduce the PIM-1 and HCl treatment for ion
stabilization of the membrane; (c, d) polymer network of protonated PBI and amine PIM-1.

PAN17−19 and polyimide (PI)20 porous supports. PIMs are a
class of microporous materials with a specific polymer structure
with straight sections followed by a cambered section by the
axle, which results in a large free volume.21 We hypothesized
that the incorporation of PIMs into a PBI membrane could
loosen its structure and increase permeance. Although nitrile
PIM-1 is soluble in many solvents, insoluble amine PIM-1 can
be obtained through the treatment with the reducing agent
borane−dimethyl sulfide complex [(CH3)2S·BH3].22 To the
best of our knowledge, this is the first report on (i) the
polymer blend approach for OSN and (ii) the application of
PIM membranes in PAS.
system. The excess K2CO3 was removed by filtration, and the crude
product was precipitated using methanol (100 mL) as antisolvent,
filtered, washed, and dried at room temperature. The powder was
dissolved in chloroform, precipitated with methanol, filtered, washed,
and dried at room temperature, yielding a yellow powder as final
product (15.0 g, 71%). 1H NMR (400 MHz, chloroform-d) δ: 6.83 (s,
2H), 6.45 (s, 2H), 2.35 (s, 2H), 2.19 (s, 2H), 1.39 (s, 3H), 1.34 (s,
3H). 13C NMR (101 MHz, chloroform-d) δ: 149.7, 146.92, 139.2,
112.3, 110.5, 109.4, 94.1, 58.8, 57.1, 43.6, 31.3, 29.9. Molecular weight
(GPC, in CHCl3): 23 kg mol−1.
Preparation and Ion Stabilization of PBI/PIM Membranes.
Polymer dope solutions were prepared by dissolving PIM-1 and PBI
in DMAc in specific ratios given in Table 1, followed by mechanical

■ EXPERIMENTAL SECTION
Materials and Methods. Novatexx 2471 polypropylene non-
Table 1. Membrane Compositions and Membrane
Treatmentsa
woven backing was purchased from Freudenberg Filtration Tech- PBI PIM-1
nologies, Germany. PBI dope solution (26.2 wt % polymer, 72.3 wt % content content viscosity BH3·SMe2 HCl
DMAc, 1.5 wt % LiCl, 27 kg mol−1) was purchased from PBI membrane (wt %) (wt %) (mPa s) treatment treatment
Performance Products, USA. All the used solvents including acetone, M0 100 0 6550 n.a.c −
acetonitrile (MeCN), borane−dimethyl sulfide, chloroform, dichloro- M1 100 0 6650 n.a. +
methane, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide M2 96 4 7600 + +
(DMF), diethyl ether, dimethyl sulfoxide (DMSO), ethyl acetate, N- M3 92 8 8900 + +
methyl-2-pyrrolidone (NMP), 2-methyltetrahydrofuran (MeTHF), M4 88 12 9800 + +
methanol (MeOH), propylene carbonate (PC), and trimethylamine
M5b 84 16 10900 n.a. n.a.
(TEA) were purchased from Sigma-Aldrich. Acetophenone, benzo-
a
phenone, triazabicyclodecene (TBD), tetrafluoroterephthalonitrile, The weight percentages refer to the polymer content of the
5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane, potas- membrane. All dope solutions were prepared using DMAc as the
sium tert-butoxide (tBuOK), and potassium carbonate (K2CO3) were solvent and had 18 wt % total polymer content. bThis membrane was
purchased from Alfa. Polystyrene markers for solute rejection found to be unstable, and it was not tested. Refer to Figure 6b for
evaluation were purchased from Agilent Technologies. All solutions further details. cn.a. = not applicable.
were prepared using Milli-Q Type II water with a resistivity of 18.2
MΩ cm at 25 °C. stirring for 2 h at 50 °C. The dope solutions were degassed for 12 h in
Synthesis of PIM-1. Synthesis of PIM-1 was performed according an incubator shaker at 45 °C. The dope solution was then cast at 45
to a literature procedure.21 3,3,3′,3′-Tetramethyl-2,2′,3,3′-tetrahydro- °C and a speed of 0.05 m s−1 on nonwoven polypropylene support
1,1′-spirobis[indene]-5,5′,6,6′-tetraol (15 g, 14.7 mmol, 1 equiv), using a casting knife set to 250 μm thickness. The wet films were
tetrafluoroterephthalonitrile (8.8 g, 14.7 mmol, 1 equiv), and K2CO3 immediately immersed in water at 21 ± 0.5 °C for phase inversion,
(18.5 g, 44.1 mmol, 3 equiv) were weighed into a round-bottomed and then the water was replaced three times (3 × 5 L). For the PIM-1
flask equipped with a Dean−Stark apparatus. DMAc (44 mL) and reduction, membranes of 52.8 cm2 area were treated with BH3·SMe2
toluene (88 mL) were added under argon. The mixture was stirred at in diethyl ether.22 The membrane was washed with 50 mL of dry
reflux temperature until the nascent water was removed from the methanol and 5 × 50 mL of dry diethyl ether to remove any water

6350 DOI: 10.1021/acsanm.8b01563

ACS Appl. Nano Mater. 2018, 1, 6349−6356
ACS Applied Nano Materials
from the membrane. The membrane was transferred into a reactor
equipped with a cooler. Dry diethyl ether (250 mL) and BH3·SMe2
(12.24 mL, 12.24 mmol, 1M) were added, and the reaction mixture
was stirred at 200 rpm for 12 h. The membrane was washed with dry
methanol, and for the ion stabilization, 1 M HCl (2 equiv of
benzimidazole, 10 mL) was added to treat the membranes, followed
by washing with 50 mL of water. The membranes were stored in Type
II water at room temperature (24 °C) in a dark place prior to testing.
The viscosity of the dope solutions was measured using an Elcometer
2300 rotational viscometer (Elcometer Limited, UK).
Membrane Stability Test. Dissolution in PAS. A membrane
piece of 50 mm × 50 mm was dried, weighed, and immersed into 250
mL of PAS such as acetone, MeCN, DMAc, DMF, DMSO, NMP, PC,
or MeTHF. The samples were placed in an incubator shaker for 7
days at 25 °C, followed by rinsing with acetone and drying under
vacuum. The solubility experiments were performed in duplicates
using independently prepared membranes.
Dissolution at Different pH. A membrane piece of 50 mm × 50
mm was immersed into a 250 mL aqueous solution having a pH of 2,
5, 6, 8, 9, 10, 11, or 12. The pH was adjusted by adding 1 M HCl or
NaOH. The samples were placed in an incubator shaker for 24 h at 25
°C, followed by rinsing with water, drying, and weighing. The dry
samples were immersed into 250 mL of DMF. The samples were
placed in an incubator shaker for 7 days at 25 °C, followed by rinsing
with acetone and drying under vacuum. The solubility experiments
were performed in duplicates using independently prepared
membranes.
Nanofiltration. Nanofiltration experiments were performed in a
cross-flow system (Figure S1) at 30 bar at room temperature with
MeTHF, MeCN, DMF, DMSO, and PC as solvents to determine
permeate flux and molecular weight cutoff (MWCO)23 curves of the
membranes. Two independently prepared membrane discs of each
type were tested, and the reported results are the mean values of these
measurements. To avoid ambiguity of the results, independently
prepared membranes were used for each solvent. The filtrations were
performed for 24 h. Steady state was reached within 6 h, and samples
were taken after 24 h. The flow rate for the retentate recirculation was
set at 1200 mL h−1 to ensure homogeneous solute concentration in
the retentate loop. The permeance and the MWCO of M4 has also
been tested at 25, 50, 75, 100, and 125 °C in DMSO following the
thermal treatment (tt) sequences described in Table 2. Each step was
performed for 24 h in DMSO at 30 bar.
Table 2. Thermal Treatment Sequences and Steps Which
Were Carried out Consecutively on the Same Membrane
Piece in DMSO at 30 bara
temperature (°C)
sequence step 1 step 2 step 3 step 4 step 5
1 (tt1) 25 50 75 100 125
2 (tt2) 125 100 75 50 25
3 (tt3) 25 50 75 100 125
4 (tt4) 125 100 75 50 25
a
The duration of each step was 24 h.
Permeate samples for flux measurements were collected at intervals
of 1 h, and samples for MWCO evaluations were taken after steady
permeate flux was achieved. MWCO values were obtained by using a
standard test solution composed of a homologous series of styrene
oligomers dissolved in the selected solvent.24 The MWCO values
were derived from the MWCO curves via linear interpolation. The
styrene oligomer mixture contained 1 g L−1 of PS 580 and PS 1300
and 0.01 g L−1 of α-methylstyrene dimer, and their concentration was
determined using a previously reported HPLC method.25 The
effective area (A) of each membrane was 52.8 cm2. The permeance
was calculated as given in eq 1.
6351
Article
J V
permeance = = = [L m−2 h−1 bar −1]
ΔP ΔPAt (1)
The permeance of each membrane was calculated by dividing the
solvent flux through the membrane (J) by the transmembrane
pressure (ΔP). The flux was obtained by measuring the volume of
solvent (V) that permeates through the membrane per membrane
area (A) per time (t). The rejection of solutes was determined to be
the ratio of its measured concentration in the permeate (Cp) and the
feed (Cf) as defined in eq 2.
ij C p yz
rejection = 100 jjj1 − zz = [%]
j z
k Cf z{
(2)
Analytical Methods. The infrared spectra were recorded from
dry membrane samples using a Thermo Fisher Nicolet iD5 ATR-
FTIR spectrometer. Atomic force microscope infrared spectroscopy
(AFM-IR) was performed on a NanoIR2 system (Anasys Instru-
ments) in contact mode at a scan rate of 0.3 Hz using a gold-coated
silicon nitride probe (Anasys Instruments, 0.07−0.4 N m−1 spring
constant, 13 ± 4 kHz resonant frequency). The amplitude of induced
cantilever oscillations was mapped using 32 coaverages per 1024
points per 1024 scan lines. The solid-state NMR measurements were
recorded on a Bruker Avance III (400 MHz) with 4 mm CPMAS
probe with the spinning rate of 10000 Hz. The liquid phase NMR
measurements were recorded on a Bruker Avance III (400 MHz)
using chloroform-d as a solvent. The average molecular mass of PIM-1
was measured by gel permeation chromatography (GPC). Analysis
was performed in CHCl3 at a flow rate of 1 mL min−1 using a
Viscotek VE2001 GPC solvent/sample module with two PL Mixed B
columns and a Viscotek TDA302 triple detector array (refractive
index, light scattering, viscosity detectors). The data were analyzed by
the OmniSec program. BET surface area measurement was performed
on an ASAP 2020 V4.00H machine using nitrogen gas at 77.451 K.
Scanning electron microscopy (SEM) measurements were performed
on a FEI Quanta 200 field emission scanning electron microscope,
and the samples were sputtered 10 nm gold/palladium coating under
an argon atmosphere using a Quorum Q150TES. The contact angle
measurements were performed on a Krüss DSA 100 drop-shape
analysis system. The viscosity for the dope solutions for membrane
casting was measured with an Elcometer 2300RV at room
temperature. Atomic force microscopy (AFM) images were acquired
in tapping mode in air using a Digital Instruments Dimension 3100
with a Bruker TESPA-V2 probe with a nominal spring constant of 37
N m−1 and a nominal tip apex radius of 7 nm. Samples were prepared
by sticking the membranes on a glass slide using double-sided tape.
For roughness calculations, three membranes of each type with an
area of 25 μm2 were scanned and analyzed with the NanoScope
Analysis software.
■
RESULTS AND DISCUSSION
Membrane Performance. The stability of membranes
was probed against polar aprotic solvents, and the weight losses
are summarized in Table 3. All the membranes were found to
be stable in acetone, MeCN, and MeTHF. The nonmodified
PBI membrane (M0) was dissolved in DMAc, DMF, NMP,
DMSO, and PC. Surprisingly, the HCl-treated PBI membrane
(M1) was not dissolved in any PAS. Literature reports on
robust PBI membranes that are stable in PAS; all employed
cross-linking with toxic reagents at elevated temper-
atures,13,26,27 although sustainable attempts are sought
after.28 It was successfully demonstrated that a simple
protonation with HCl can provide a simple and green
alternative to covalent cross-linking of PBI membranes.
Figure 2a shows the permeance of M1−M4 membranes in
PAS. The permeance increased with the increasing amine PIM-
1 content due to its microporosity and increased hydro-
philicity. The number of amine groups is increasing with the
DOI: 10.1021/acsanm.8b01563
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Table 3. Percentage Weight Loss of Membrane in Polar of 420 g mol−1 in DMSO. M1 has the highest MWCO in each
Aprotic Solvents solvent ranging from 510 to 660 g mol−1. Interestingly, the
incorporation of only 4 wt % PIM-1 resulted in a significantly
M0 M1 M2 M3 M4
tighter membrane (M2) as the MWCO values decreased by up
acetone 0 ± 0 0 ± 0 0 ± 0 0 ± 0 0 ± 0 to 67% in all the solvents compared to M1. However, further
MeCN 0 ± 0 0 ± 0 0 ± 0 0 ± 0 0 ± 0 addition of PIM-1 increased the MWCO but still provided
DMAc 100 ± 0 1 ± 0a 0 ± 0a 0 ± 0a 0 ± 0a tighter membranes (M3−M4) than M1 in all the solvents.
DMF 100 ± 0 1 ± 0a 0 ± 0a 0 ± 0a 0 ± 0a Considering all membranes, the lowest polarity solvent
NMP 100 ± 0 1 ± 0a 0 ± 0a 0 ± 0a 0 ± 0a (MeTHF) has the narrowest MWCO distribution covering
DMSO 100 ± 0 2 ± 0a 0 ± 0a 0 ± 0a 0 ± 0a the 400−510 g mol−1 range, while the highest polarity solvent
PC 89 ± 6 0 ± 0 0 ± 0 0 ± 0 0 ± 0
(PC) has the widest MWCO distribution ranging from 200 to
± ± ± ± ±
a
MeTHF 0 0 0 0 0 0 0 0 0 0
600 g mol−1. These membranes enable a wide operation range
Faint discoloration of the solvent occurred, which is speculated to be for processing PC-based solutions, which could facilitate the
from the leaching of some smaller oligomers from the membranes. uptake of this green solvent by the industrial sector. The
aforementioned phenomenon is speculated to be the result of
the nonlinear change in the microporosity and interconnec-
tivity of the two polymers at different concentrations (4, 8, and
12 wt %).
The thermal processing and thermal resistance of mem-
branes could open new opportunities for liquid processing.
The changes of permeance and MWCO of M4 as a function of
temperature in DMSO were investigated (Figure 3). At each
temperature a stable but different performance was observed
for tt1 (see Table 2). The permeance increased from 1.4 to 2.0
L m−2 h−1 bar−1 as the temperature was gradually increased
from 25 to 125 °C (Figure 3a). However, the consecutive

Figure 2. Permeance (a) and MWCO (b) values for M1 (0 wt %

amine PIM-1), M2 (4 wt % amine PIM-1), M3 (8 wt % amine PIM-
1), and M4 (12 wt % amine PIM-1) in different PAS measured at 25
°C. Refer to the Supporting Information for the rejections and cutoff
curves.

increasing amine PIM-1 content (M2 → M3 → M4), which

increases the hydrophilic characteristics of the membrane. The
lowest permeance has been measured in the case of M1 in
MeTHF and the highest in the case of M4 in PC with 0.37 ±
0.04 and 2.4 ± 0.1 L m−2 h−1 bar−1, respectively. PC has the
highest permeance since the membrane material favors
hydrophilic solvents, and vice versa MeTHF has the lowest Figure 3. Permeance (a) and MWCO (b) values for M4 as a function
permeance. Refer to Table S4 in the Supporting Information of temperature ranging from 25 to 125 °C measured in DMSO at 30
for the solvent properties. Figure 2b shows the measured bar. Refer to Table 2 for the thermal treatment sequences (tt1−4).
MWCO for M1−M4 membranes in PAS. M2 has the lowest Permeance as a function of viscosity (c) from 25 to 125 °C measured
MWCO with 190 g mol−1 in PC; however, M2 has an MWCO in DMSO at 30 bar.

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ACS Applied Nano Materials Article

Figure 4. Effect of pH on the protonation and stability of the membranes. The latter is expressed as percentage weight loss after immersion into
DMSO. Refer to the Supporting Information for the details of the pKa analysis.

Figure 5. Chemical characterization of the membranes: (a) FTIR spectra of PIM-1 and M0−M4 membranes; (b) solid-state NMR of M0, M1, and
M4. The asterisks, (s), and (b) denote the peaks caused by the spinning, the stretching, and bending frequencies, respectively.

decrease (tt2)−increase (tt3)−decrease (tt4) in temperature
revealed a different but consistent performance. The
permeance change was found to have a linear correlation
with the solvent viscosity (Figure 3c), which suggests that the
system is in accordance with Darcy’s law and the pore-flow
model.29 The thermal treatment resulted in a tighter
membrane with lower permeance and MWCO. The MWCO
considerably decreased from 620 to 360 g mol−1 during tt1 and
then further decreased from 360 to 320 g mol−1 during tt2−4
(Figure 3b). It is speculated that these results are due to the
combined effects of swelling, accelerated aging, and thermal
rearrangement of the polymer blend. The literature on thermal
treatment of membranes for liquid separations is scare and
contradictory as different observations were made.30−33
Besides varying the PBI/PIM-1 polymer blend composition,
6353
the thermal treatment of the membranes enables fine-tuning
the separation performance at a cost of decreased permeance.
Further fine-tuning of membrane performance could be
achieved via altering the phase inversion parameters, such as
the temperature.
Physical aging takes place in every polymer; however, for
glassy polymers with high free volume such as PIM-1,
accelerated physical aging occurs.34 The aging of PIM-based
membranes was studied for 3−8 days in heptane, ethanol, and
THF.17−20 The aging of M4 in DMSO was studied over 3
weeks of continuous operation with a 3 months shelf storage in
DMSO. Over this time, the MWCO and the permeance
decreased approximately 6% and 1%, respectively. Refer to the
Supporting Information for the experimental details and the
data.
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ACS Applied Nano Materials Article

Table 4. Elemental Composition and Degree of Protonation (α) for the Membranesa
membrane C (wt %) H (wt %) N (wt %) Cl (wt %) α (%)
M0 77.91/77.86 3.92/3.95 18.17/18.14 0.00/0.00 0
M1 63.01/63.25 3.70/3.71 14.70/14.75 18.60/18.25 98
M2 63.06/63.17 3.78/3.81 14.31/14.33 18.38/18.22 99
M3 63.11/63.07 3.85/3.87 13.93/13.96 18.16/18.14 100
M4 63.17/63.12 3.93/3.97 13.55/13.57 17.94/17.91 100
a
The first value is calculated for pristine PBI (M1) and assuming 100% protonation for M1−M4, while the second value is measured with
elemental analysis.

Figure 6. Membrane morphology: (a) typical AFM height image of M0−M4 with scan size of 10 μm × 10 μm; (b) AFM-IR of M5, generated from
the IR intensity at 1373 cm−1 as a characteristic peak of amine PIM-1 (color; red represents higher intensity while blue represents lower intensity)
superimposed on the AFM height image (contour) of the same area; (c, d) SEM surface images for typical M0−M4 membranes (c) and for M5
(d); (e, f) SEM cross-section images for typical M0−M4 membranes (e) and M5 (f). All SEM images were taken at 10K magnification. Refer to the
Supporting Information for the characterization of each membrane.

Owing to the ion-stabilization methodology, acids and bases
in the solution could adversely affect the stability of the
membranes. The pKa value of each amine group in the
membranes, and therefore their protonation/deprotonation,
were estimated using MarvinSketch (refer to the Supporting
Information). Figure 4 shows the effect of pH on the
protonation of the polymers as well as the results for the
stability test. In line with the predictions, the membranes were
found to be stable under both acidic (pH < 6) and basic (pH >
11) conditions. However, at pH = 6−10 the membranes were
dissolved due to the solubility of the neutral PBI, which is the
main polymer component of the membranes. Organic bases
are often used in PAS to perform various synthetic trans-
formations, and therefore the stability of membranes was also
demonstrated in the presence of TBD, TEA, and tBuOK in
DMSO. Refer to the Supporting Information for the MWCO
and permeance data in these solutions.
Chemical and Morphological Characterization. Figure
5a shows the FTIR spectra for the PIM-1 and the M0−M4
membranes. Owing to the planar cyclic and aromatic part of
PBI, the spectra of M0−M4 are composed of narrow peaks
between 2000 and 1000 cm−1 corresponding to the N−H and
C−N deformation modes (δN−H and δC−N). The characteristic
aromatic C−H stretching frequencies were found between
2900 and 3050 cm−1 as weak compact peaks (νC−H). The
characteristic aromatic and CN stretching modes were
found around 1650 cm−1 as medium wide peaks (νC=N). The
compact peaks between 1200 and 1550 cm−1 indicate the C−
6354
C and C−H of the in-plane ring vibrational and breathing
vibrational frequencies of the aromatic rings (νC−H and νC−C).
The strong peak at 802 cm−1 belongs to the heterocyclic ring
vibration (νC−H ). The characteristic CN stretching
frequency mode was found at 2240 cm−1 as a low compact
peak (νC≡N). The aforementioned peaks are missing in the
membranes containing amine PIM-1 (M2−M4), confirming
the successful reduction of the nitrile group. The aromatic
ether C−O stretching frequency mode was found at 1008 cm−1
as a strong narrow peak (νC−O). The highlighted part in Figure
5a indicates the main difference between the original PBI and
its polymer blend with the amine PIM-1. Owing to the salt
formation, characteristic new peaks can be found between
2500 and 2750 cm−1.
Figure 5b shows the solid-state NMR measurements for M0,
M1, and M4. The spectrum of the PBI (M0) correlates to the
NMR spectra reported in the literature. As a result of the HCl
treatment, the peaks at 110, 121, and 128 ppm were slightly
shifted downfield, and the original 150 and 141 ppm peaks
were convoluted. The spectrum of the M4 membrane is similar
to M1, with the additional peaks at 47 and 57 ppm
corresponding to the aliphatic carbon atoms in the amine
PIM-1.
Elemental analysis was used to reveal the elemental
composition and the degree of protonation (Table 4).
Chlorine was not found in M0, which confirms the complete
removal of the LiCl stabilizer found in the commercial PBI
used to prepare the dope solution. The degree of protonation
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ACS Applied Nano Materials
(α) is defined as the ratio of protonated amine groups and its
theoretical maximum. When all the protonizable groups are
protonated with HCl, the degree of protonation is 100%. Refer
to the acidic pH region of Figure 4 and Schemes S3 and S4 for
the protonated structures. α was found to be 98−100% for all
the HCl-treated membranes (M1−M4), which was expected
based on the pKa predictions and previous literature.22
The membrane morphology was characterized by the SEM
surface, cross section, and AFM measurements (Figure 6).
Both AFM height images and SEM images revealed similar
morphologies for M0−M4 membranes (Figure 6a,c,e).
However, the SEM revealed the presence of nano- and
microspheres in M5, which contains 16 wt % amine PIM-1
(Figure 6d,f). The phase separation behavior of M5 was further
investigated with AFM-IR at 1373 cm−1 infrared wavelength
(one of the characteristic peaks of amine PIM-1), which
confirmed the spheres to be amine PIM-1, as it revealed that
the spheres have higher IR intensity (Figure 6b). The
aggregation of PIM-1 at higher concentrations limits its
addition in the polymer blend. Employing different types of
solvent or cosolvents, or increasing the temperature for the
preparation of the dope solution and the film casting, could
increase the solubility of PIM-1, which would allow
membranes with higer PIM-1 content.
The uniqueness of the PIM-based materials is the high
surface area derived from the rigid structure of the polymer.
Therefore, surface area measurement was performed to further
investigate the effect of PIM content on the membranes (Table
5). The surface area of M1 was found to be 18.9 m2 g−1, which
Table 5. Effect of PIM-1 Addition on the BET Surface Area
and Hydrophilicity of the Membranesa
membranes
M1 M2 M3 M4
BET surface 18.9 ± 1.1 35.4 ± 2.1 44.4 ± 1.8 56.1 ± 2.2
area (m2 g−1)
contact angle 61 ± 2 51 ± 2 41 ± 2 36 ± 2
(deg)
The PIM-1 has 705 m2 g−1 surface area; refer to the Supporting
a
Information for further characterization.
gradually increased with the incorporation of PIM-1 into the
membrane and reached 56.1 m2 g−1 (M4). The surface area
shows a linear correlation with the increasing amount of amine
PIM-1 in the membrane, which could explain the increasing
permeance (Figure 2a). Based on the surface area of PIM-1
(705 m2 g−1) and M1 (18.9 m2 g−1), the theoretical surface
area for M2−M4 was estimated to be 46, 73, and 101 m2 g−1,
respectively. The observed lower values are speculated to be
the result of the PIM-1 reduction, protonation, and
entanglement of the PBI and PIM-1 polymer chains. Higher
amine PIM-1 content increased the hydrophilicity of the
membranes, which was demonstrated by the decreasing
contact angle from 61° (M1) to 36° (M4). The increase in
both the hydrophilicity and surface area resulted in a higher
transport rate of polar molecules from the bulk to the surface
and subsequently increased the permeance of PAS (see Figure
2a). Decoupling of these effects is a challenge yet to be solved.
■
CONCLUSIONS
Polymer blend membranes, for solvent-resistant nanofiltration
in polar aprotic solvents, have been fabricated for the first time
6355
Article
using PBI and amine PIM-1. Ion stabilization of PBI and PBI/
PIM-1 membranes via simple HCl treatment was successfully
demonstrated. The novel stabilization approach eliminates the
use of cumbersome chemical cross-linking. The incorporation
of PIM-1 into the membranes improved the permeance of the
membranes up to 4 times and simultaneously decreased the
MWCO. Filtration studies covering 3 months revealed a
moderate membrane aging with performance change of up to
6%. A comprehensive thermal treatment study of the
membranes revealed stable but anomalous performance up
to 125 °C. Propylene carbonate was identified as a promising
green solvent for replacement of conventional PAS in chemical
manufacturing due to its facile processing with membranes.
Based on the results, ion stabilization could not only open new
possibilities for the fabrication of robust OSN membranes but
also could be exploited for the fabrication of polymer
coatings,35 batteries,36,37 and electromembranes.38,39
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsanm.8b01563.
NMR spectra, SEM and AFM images, AFM-IR analysis,
pKa predictions, membrane stability test, aging study,
reaction schemes, PIM-1 characterization, rejections and
cutoff curves (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail gyorgy.szekely@manchester.ac.uk, Tel +44 (0) 161
306 4366.
ORCID
Gergo Ignacz: 0000-0002-7227-3070
Fan Fei: 0000-0003-0548-5775
Gyorgy Szekely: 0000-0001-9658-2452
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors express their gratitude to Mr. Levente Cseri (The
University of Manchester) for the technical assistance with the
solid-state NMR.
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