membranes
Article
Synthesis of Porous BPPO-Based Anion Exchange Membranes
for Acid Recovery via Diffusion Dialysis
Muhammad Imran Khan 1 , Abdallah Shanableh 1 , Majeda Khraisheh 2, *






Citation: Khan, M.I.; Shanableh, A.;
Khraisheh, M.; AlMomani, F.
Synthesis of Porous BPPO-Based
Anion Exchange Membranes for Acid
Recovery via Diffusion Dialysis.
Membranes 2022, 12, 95. https://
doi.org/10.3390/membranes12010095
Academic Editor: Yan Zhao
Received: 28 December 2021
Accepted: 12 January 2022
Published: 16 January 2022
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Attribution (CC BY) license (https://
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4.0/).
Membranes 2022, 12, 95. https://doi.org/10.3390/membranes12010095
and Fares AlMomani 2
1 Research Institute of Sciences and Engineering (RISE), University of Sharjah, Sharjah 27272,
United Arab Emirates; raoimranishaq@gmail.com (M.I.K.); shanableh@sharjah.ac.ae (A.S.)
2 Department of Chemical Engineering, College of Engineering, Qatar University, Doha P.O. Box 2713, Qatar;
falmomani@qu.edu.qa
* Correspondence: m.khraisheh@qu.edu.qa
Abstract: Diffusion dialysis (DD) is an anion exchange membrane-based functional separation
process used for acid recovery. TMA (trimethylamine) and BPPO (brominated poly(2,6-dimethyl-1,4-
phenylene oxide) were utilized in this manuscript to formulate AEMs (anion exchange membranes)
for DD (diffusion dialysis) using the phase-inversion technique. FTIR (Fourier transfer infrared)
analysis, proton NMR spectroscopy, morphology, IEC (ion exchange capacity), LER (linear expansion
ratio), CR (fixed group concentration), WR (water uptake/adsorption), water contact angle, chemical,
and thermal stability, were all used to evaluate the prepared membranes. The effect of TMA content
within the membrane matrix on acid recovery was also briefly discussed. It was reported that
porous AEMs have a WR of 149.6% to 233.8%, IEC (ion exchange capacity) of 0.71 to 1.43 mmol/g,
CR (fixed group concentration) that ranged from 0.0046 mol/L to 0.0056 mol/L, LER of 3.88% to
9.23%, and a water contact angle of 33.10◦ to 78.58◦ . The UH (acid dialysis coefficients) for designed
porous membranes were found to be 0.0043 to 0.012 m/h, with separation factors (S) ranging from
13.14 to 32.87 at the temperature of 25 ◦ C. These observations are comparable to those found in the
DF-120B commercial membrane with UH of 0.004 m/h and S of 24.3 m/h at the same temperature
(25 ◦ C). This porous membranes proposed in this paper are excellent choices for acid recovery through
the diffusion dialysis process.
Keywords: BPPO; diffusion dialysis; trimethylamine; acid recovery; porous anion exchange membrane
(AEM)
1. Introduction
Metal etching, pickling, and stripling processes generate a lot of waste solutions
containing inorganic acids [1–5], whereas organic acid-containing waste solutions are cre-
ated by fermentation, food, leather, and pharmaceutical corporations [1,2,6–8]. Different
processes, such as neutralization [9–11], coagulation and flocculation [12], extraction [13],
and the ion exchange process [14–19], can be used to recover the acids. In the chemical
and biochemical sectors, ion exchange membranes (IEMs) play an integral role [20]. Ion
exchange membranes (IEMs) that are delicate films (usually very thin) composed of im-
mobile positively or negatively charged functional groups and counter ions are gaining
popularity since they make separation processes simpler, more productive, and less expen-
sive. AEMs (anion exchange membranes) and CEMs (cation exchange membranes) are
two major categories of IEMs. AEMs have lately attracted considerable attention because
they can effectively retrieve acid wastes from various industries such as mining, metal
manufacturing, painting, and agriculture [21–24].
The DD (diffusion dialysis) process is a versatile strategy that utilizes (AEMs) anion
exchange membranes for the extraction and recovery of acids [25–31]. To be more specific,
the diffusion dialysis process depends on a concentration gradient for removing and
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Membranes 2022, 12, 95 2 of 17
Membranes 2022, 12, 95 2 of 16

the diffusion dialysis process depends on a concentration gradient for removing and pu-
rifying thethe
purifying acid ororalkali
acid alkaliwaste
wastesolutions
solutionsusing
usingthe
the ion-exchange
ion-exchange membrane separation
method [8,23]. High
High energy savings [32,33], environmental safety [17], and continuous
continuous
operation [34] are all advantages of the DD process. When producing chemicals, the acids
can be recycled and reused, whereas the waste solution’s residual products, such as metal
ions, can be eliminated
eliminated immediately [8]. The diffusion dialysis mechanism is shown in
Figure 1 by the separation of HCl from
from its
its inlet
inlet solution.
solution.

Figure 1. Graphical representation of the diffusion dialysis process through the anion exchange
Figure 1. Graphical representation of the diffusion dialysis process through the anion exchange
membrane separation process of HCl from its inlet feed solution.
membrane separation process of HCl from its inlet feed solution.
A concentration gradient exists between the feed and outlet sides, as seen in Figure
A concentration gradient exists between the feed and outlet sides, as seen in Figure 1.
1. As a result,
As a result, bothboth the hydrogen
the hydrogen ions ions (cations)
(cations) and theandchloride
the chloride ions (anions)
ions (anions) diffusediffuse
across
across
the the exchange
anion anion exchange membrane.
membrane. Although
Although beingbeing positively
positively charged,
charged, hydrogen
hydrogen ionsions
are
are capable
capable of passing
of passing across
across thetheAEM AEM dueduetototheir
theircompact
compactsize,
size,high
highmobility,
mobility, and
and lower
lower
valence state.
valence state.Metals
Metalsininthe
thefeed
feedsolution
solution dodonotnotpasspass through
through the the
AEM,AEM, so they
so they are re-
are rejected.
jected. From the outlet side, the HCl is extracted. As a result, the acid
From the outlet side, the HCl is extracted. As a result, the acid is successfully extracted is successfully ex-
tracted from the inlet solution. The use of AEM to recover acid through
from the inlet solution. The use of AEM to recover acid through diffusion dialysis has been diffusion dialysis
has been extensively
extensively proposedproposed
and applied andaround
appliedthearound
world. the world.
The numberThe of
number of publications
publications per year
per year in this area are shown
in this area are shown below in Figure 2.below in Figure 2.
There is
There is aa general
general upward
upward trendtrend inin the
the number
number of of publications
publications each
each year, as seen
year, as seen in
in
Figure 2. This demonstrates that acid recovery through the diffusion
Figure 2. This demonstrates that acid recovery through the diffusion dialysis process usingdialysis process us-
ingAEM
an an AEMhas has received
received a lotaoflotattention
of attention in last
in the the decade.
last decade.
Because of their prominence in DD, anion exchange membranes membranes have have received
received con-
con-
siderable attraction [23,26–28,31,35]. Polymers such as PS PS (Polystyrene),
(Polystyrene), PSf
PSf (Polysulfone),
(Polysulfone),
and BPPO
BPPO (brominated
(brominatedpoly(2,6-dimethyl
poly(2,6-dimethyl1,4-phenylene
1,4-phenylene oxide))
oxide))make up up
make thethe
bulkbulk
of ho-
of
mogenous acid recovery AEMs [8] . Presently, the dense membranes
homogenous acid recovery AEMs [8]. Presently, the dense membranes make up the plu- make up the plurality
of AEMs
rality used in
of AEMs acidinrecovery
used via diffusion
acid recovery dialysisdialysis
via diffusion [36]. Direct
[36]. evaporation is used to
Direct evaporation is
typically
used manufacture
to typically the polymers’
manufacture solutionsolution
the polymers’ (homogeneous membrane)
(homogeneous such as such
membrane) poly(p-
as
poly(p-phenylene oxide), polystyrene, and polysulfone [8], or the copolymerization of
Membranes 2022, 12, 95 3 of 17

Membranes 2022, 12, 95 3 of 16

phenylene oxide), polystyrene, and polysulfone [8], or the copolymerization of monomer
units within the pores of a porous membrane surface that has already been formed (het-
erogeneousunits
monomer membrane)
within the[37–40].
poresThey
of aare, however,
porous often thick
membrane surfaceandthat
compact (severalbeen
has already tens
or hundreds
formed of micrometers),
(heterogeneous which [37–40].
membrane) can obstruct
Theythe
are,transportation
however, often of thick
ions into
andthe mem-
compact
brane [8].
(several Theoracid
tens dialysisofcoefficient
hundreds (UH) of
micrometers), the BPPO-based
which can obstructcommercial membrane
the transportation DF-
of ions
120B,the
into formembrane
instance, is[8].
indeed just 0.004
The acid m/hcoefficient
dialysis at 25 °C [41].
(UHDue) of to
thepoor permeation
BPPO-based concerns,
commercial
this study centered
membrane DF-120B,onforincorporating a new feature
instance, is indeed intom/h
just 0.004 at 25 ◦ C [41].
the membrane matrix.
Due The starting
to poor per-
material concerns,
meation was chosen thistostudy
be polymers
centered that are hydrophilic
on incorporating a newin nature,
feature typically polyvinyl
into the membrane
alcohol The
matrix. (PVA), and the
starting assistant
material wasfunctional
chosen to groups of –Si–OH
be polymers that areand –C–OH were
hydrophilic integrated
in nature, typ-
ically
onto itpolyvinyl
[42,43]. Atalcohol
20 °C,(PVA), and the assistant
the membranes enhanced functional
their UH groups
values fromof –Si–OH and –C–OH
0.007 m/h to 0.015
were integrated
m/h. [43]; ontothe
however, it [42,43]. At 20 ◦ C, the
key disadvantage membranes
of the membranes enhanced
based ontheir
PVA UHwas
values
thatfrom
they
0.007
swelledm/h to 0.015
a lot in them/h.
water, [43]; however,
making the
their key disadvantage
long-term stability aofconcern.
the membranes based
To address on
these
PVA was that
difficulties, they
tiny swelled
alkoxy a lotsuch
silanes in the
as water, making their
tetraethoxysilane long-term
(TEOS) stability
or multi a concern.
silicon copoly-
To
mer address
forming these difficulties,
groups were usedtiny alkoxy silanes such
to functionalize as tetraethoxysilane
and cross link the PVA (TEOS)
mainorchains
multi
silicon copolymer forming groups were used to functionalize
[43,44]. When we switched from dense membrane to porous membrane processing, and cross link the PVA main
we
chains
had to [43,44].
change When we switched
our strategy to solvefrom dense
these issues.membrane to porous membrane processing,
we had to change our strategy to solve these issues.

6000
5250
4960 4850 4800
5000 4560 4690
4320 4320 4210
4000 3420
Publication number

2970
3000

2000 1550

1000

0
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021

Publication year

Figure 2. A
Figure 2. A brief
briefpost-2010
post-2010timeline
timelinedepicting
depictingthe number
the numberof of
associated academic
associated publications
academic for the
publications for
acid retrieved through diffusion dialysis process with anion exchange membranes (Available
the acid retrieved through diffusion dialysis process with anion exchange membranes (Available online:
Google Scholar Scholar
online: Google (12 December 2021). 2021).
(12 December

BPPO
BPPO waswas chosen
chosen asas the
the polymer
polymer matrix
matrix since
since the
the feasibility
feasibility of
of making
making aa porous
porous
membrane
membrane out of a hydrophobic polymer could be established. Figure 3 below
out of a hydrophobic polymer could be established. Figure 3 below depict
depict the
the
three-dimensional
three-dimensional structure
structure of
of the
the BPPO:
BPPO:
We
We recognize
recognize that
that the
the porous
porous structure
structure lowers
lowers ion
ion transport
transport resistance,
resistance, whereas
whereas the
the
polymer increases membrane durability. Apart from DD, porous
polymer increases membrane durability. Apart from DD, porous membranes membranes are frequently
are fre-
used in several
quently used in different methods.
several different These membranes,
methods. for example,
These membranes, are typically
for example, used
are typically
in membrane processes that depend on pressure gradients such as ultrafiltration and
used in membrane processes that depend on pressure gradients such as ultrafiltration and
nanofiltration. Moreover, for desalination purposes, to fabricate porous composite ion-
nanofiltration. Moreover, for desalination purposes, to fabricate porous composite ion-
exchange membranes, other research teams employed a two-step approach of phase-
exchange membranes, other research teams employed a two-step approach of phase-in-
inversion [45,46]. Despite the fact that these micropores do not penetrate through the entire
version [45,46]. Despite the fact that these micropores do not penetrate through the entire
membrane, they can help HCl diffusion greatly [47].
membrane, they can help HCl diffusion greatly [47].
This paper describes the phase-inversion process used to formulate and characterize
This paper describes the phase-inversion process used to formulate and characterize
BPPO-based porous anion exchange membranes in ethanol medium using the reaction of
BPPO-based porous anion exchange membranes in ethanol medium using the reaction of
BPPO and TMA. By varying the concentration for TMA (Figure 4) into the membrane matrix,
BPPO and TMA. By varying the concentration for TMA (Figure 4) into the membrane
the porous AEMs have been developed with different physicochemical characterizations. In
batch mode, they were compared to the commercial DF-120B membrane for acid recovery
through the DD process.
 matrix, the porous AEMs have been developed with different physicochemical character-
matrix, the
izations. porous
In batch AEMs
mode, have
they been
were developed
compared to with different physicochemical
the commercial character-
DF-120B membrane for
izations. In batch mode, they were compared
acid recovery through the DD process. to the commercial DF-120B membrane for
acid recovery through the DD process.
Membranes 2022, 12, 95 4 of 16

Figure 3. A three dimensional (3D) structure of brominated poly (2,6-dimethyl 1,4-phenylene oxide)
Figure
Figure 3.
(BPPO). Athree
3. A threedimensional
dimensional(3D)
(3D)structure
structure
of of brominated
brominated poly(2,6-dimethyl
poly 1,4-phenylene
(2,6-dimethyl 1,4-phenylene ox-
oxide)
ide) (BPPO).
(BPPO).

Threedimensional
Figure4.4.Three
Figure dimensional(3D)
(3D)structure
structureof
ofTrimethylamine
Trimethylamine(TMA).
(TMA).
Figure 4. Three dimensional (3D) structure of Trimethylamine (TMA).
2. Experimental
2. Experimental
2.1. Materials
2. Experimental
2.1. Materials
Tianwei Membrane Co. Ltd., Shandong, China, provided brominated poly(2,6-dimethyl-
2.1. Tianwei
Materials
1,4-phenyleneMembrane
oxide) (BPPO) Co. Ltd.,
and anShandong, China,membrane
anion exchange provided brominated poly (2,6-di-
that is commercially avail-
able; DF-120B (part of the DF-120 series). DF-120B is composed primarily of poly
Tianwei
methyl-1,4-phenylene Membrane oxide)Co. Ltd.,
(BPPO) Shandong,
and an China,
anion provided
exchange brominated
membrane that (2,6-di-
is commer-
quaternized
methyl-1,4-phenylene
cially available; DF-120B
poly(2,6-dimethyl-1,4-phenylene oxide)
(part(BPPO)
of oxide)and
the DF-120 an series).
(QPPO) anion
and exchange
DF-120B membrane
polyester is acomposed
as substrate.that is commer-
primarily
Typical of
char-
cially available;
quaternized
acteristics of poly DF-120B (part of the
this(2,6-dimethyl-1,4-phenylene DF-120
membrane include water uptake series). DF-120B
oxide) (QPPO)
of 74.2% and is
with composed
polyester primarily
IEC ofas0.83
a substrate.
mmol/g. of
quaternized
Typical
Trimethylamine poly(TMA),
characteristics (2,6-dimethyl-1,4-phenylene
of ethanol,
this membrane include
hydrochloric oxide)
water
acid (QPPO)
(HCl),uptake and polyester
of 74.2%
ferrous chloride withasIEC
a substrate.
(FeCl 2 ·of
4H0.83
2 O),
Typical characteristics
mmol/g.
sodium Trimethylamine
chloride, of this
potassium membrane
(TMA),
permanganate include
ethanol, (KMnO water
hydrochloric
4 ), uptake
andacid
sodiumof 74.2%
(HCl), with
ferrous
carbonate IEC of
chloride
(Na 2
0.83
CO 3)
mmol/g.
(FeCl
were2·obtainedTrimethylamine
4H2O), sodium (TMA),
chloride, potassium
from Sinopharm ethanol, hydrochloric
Chemical permanganate
Reagent Co. Ltd., acid
(KMnO
China. (HCl),
4), and ferrous
The sodium chloride
carbonate
rest of the reagents
(FeCl
(Na
used2CO 2·4H
in 3the2O),
) were sodium
obtained
experiments chloride,
fromof
were potassium
Sinopharm permanganate
Chemical
analytical grade and Reagent (KMnO 4),
Co. Ltd.,
commercially andChina.
availablesodium
from carbonate
The rest of
domestic
(Na
the 2CO3)reagent
chemical
reagents were
usedobtained
in from Sinopharm
manufacturers.
the experiments These ofChemical
reagents
were were Reagent
analytical used
grade Co.commercially
without
and Ltd., China.
further The
purification. rest In
available of
the reagents
addition,
from domestic used
throughout in the
chemical the experiments
experiment,
reagent were of analytical
deionized
manufacturers. grade
waterreagents
These (DI and
water)
were commercially
was withoutavailable
used.
used further
from domestic
purification. In chemical
addition,reagent manufacturers.
throughout These reagents
the experiment, deionizedwere waterused(DI
without
water)furtherwas
2.2.
used. Preparation
purification. In of Porous
addition, Membranes
throughout Based
theon BPPO
experiment, deionized water (DI water) was
used.The procedure of phase-inversion was used for the fabrication of the porous AEMs,
as mentioned previously in our studies [41,48]. Firstly, 3 g of BPPO (brominated poly(2,6-
dimethyl-1,4-phenylene oxide)) was dissolved into NMP (N-Methyl-2-pyrrolidone) solvent
at ambient temperature in a typical procedure. To obtain porous AEMs with different
physicochemical properties, different amounts of trimethylamine (TMA) varying from
0.15 to 0.30 g were applied to the casting solution according to Table 1. The reaction mixture
was stirred overnight at 40 ◦ C to accelerate the reaction between BPPO and trimethylamine.
The solution was subsequently poured onto a glass plate and immediately immersed in an
ethanol medium (Figure 5). The membranes were cleaned by infusing them in water for
two days straight, consecutively. The membranes were given the labels M1, M2, M3, and
Membranes 2022, 12, 95 5 of 17
Membranes 2022, 12, 95 5 of 17

Membranes 2022, 12, 95 5 of 16

2.2. Preparation of Porous Membranes Based on BPPO
2.2. Preparation of Porous Membranes Based on BPPO
The procedure of phase-inversion was used for the fabrication of the porous AEMs,
M4 The procedure
as mentioned
according to of phase-inversion
previously in our
the quantity of amine was used
studiesutilized.
[41,48]. forformulated
Firstly,
The the
3 gfabrication
of BPPO of the porous
(brominated
BPPO-based AEMs,
poly(2,6-
membrane’s
as mentioned previously
dimethyl-1,4-phenylene
chemical composition is also in our
oxide))
shown studies [41,48].
wasindissolved Firstly, 3 g of BPPO (brominated
Figure 6. into NMP (N-Methyl-2-pyrrolidone) sol- poly(2,6-
dimethyl-1,4-phenylene
vent at ambient temperature oxide)) was dissolved
in a typical procedure.intoToNMP
obtain (N-Methyl-2-pyrrolidone)
porous AEMs with different sol-
vent
Table at ambient
physicochemical temperature
1. Composition, properties,
ion exchangein a typical
different procedure.
amounts
capacity, To obtain
of trimethylamine
fixed group porous
concentration, water AEMs
(TMA) with
varying
uptake, different
from
and mem-
physicochemical
0.15
branestoswelling
0.30 g were properties,
applied to
of membranes M1different
the casting
to M4. amounts
solutionofaccording
trimethylamine
to Table(TMA) varying mix-
1. The reaction from
0.15 to 0.30 g were applied to the casting solution according
ture was stirred overnight at 40 °C to accelerate the reaction between BPPO−and to Table 1. The reaction mix-
trime-
Sr. No BPPO (g) TMA at (g)40 °C IECto(mmol/g) W LER 3 (mol/L)
× 10 and
ture was stirred overnight accelerate theR (%)
reaction (%)
between CBPPO trime-
thylamine. The solution was subsequently poured onto a glass plate and immediately im-
thylamine.
M1 in an
mersed The 3 solution
ethanol was
0.15 subsequently
medium (Figure 0.71 poured
5). The onto a glass
149.60
membranes plate
were3.88
cleanedandby immediately
4.74 them
infusing im-
M2
mersed in an 3
ethanol 0.20
medium (Figure 0.98
5). The 170.45
membranes were 5.0
in water for two days straight, consecutively. The membranes were given the labels M1,cleaned by 5.75
infusing them
in M3
M2, water for two
M3, and M4
3 days straight,
according
0.25
to the
1.20
consecutively.
quantity The 196.42
of amine membranes
utilized. The
5.98
were given the
formulated
6.10
labels M1,
BPPO-based
M4 3 0.30 1.43 233.80 9.23 6.12
M2, M3, and M4 according to the quantity
membrane’s chemical composition is also shown in Figure 6.of amine utilized. The formulated BPPO-based
membrane’s chemical composition is also shown in Figure 6.

Figure 5. Illustration of phase-inversion method for the fabrication of anion exchange membrane.
Figure5.5.Illustration
Figure Illustrationof
ofphase-inversion
phase-inversionmethod
methodfor
forthe
thefabrication
fabricationof
ofanion
anionexchange
exchangemembrane.
membrane.

Figure 6. Designing of anion exchange membranes based on BPPO.

Figure6.6.Designing
Figure Designingof
ofanion
anionexchange
exchangemembranes
membranesbased
basedon
onBPPO.
BPPO.

2.3. Characterizations
2.3.1. Instrumentations
Using an FTIR spectrometer (Vector 22, Bruker, Billerica, MA, USA) with a resolution
of 2 cm−1 and a total spectral range of 4000–400 cm−1 , the attenuated total reflectance
Membranes 2022, 12, 95 6 of 16

(ATR) technique was used to record the FTIR spectra for the dry membranes. The chemical
structures of the BPPO and prepared membranes were also identified using a proton NMR
(DMX 300 NMR spectrometer operating at 300 MHZ). With a Shimadzu TGA-50H analyzer,
TGA was conducted on the developed membranes in the range of temperatures from 25 ◦ C
to 700 ◦ C under nitrogen flow and a heating rate of 10 ◦ C/min. The structure or morphology
of the membrane was examined using a field emission scanning electron microscope
(FE-SEM, Sirion200, FEI Company, Hillsboro, OR, USA). Dry membranes were analyzed
with their surface and cross-sectional views. As representative cases, SEM illustrations
of various porous BPPO-based membranes were displayed. For ease of handling, the
formed membranes’ water contact angle was calculated at room temperature. A sessile
drop method was used to obtain contact angle values from a one-contact-angle goniometer
(SL200B, Shanghai, China) configured with video capture. In total, 40 µL of water was
sprayed onto a membrane that was dried using a micro-syringe in a concentrated water
vapor environment.

2.3.2. Ion Exchange Capacity

The ion exchange capacity (IEC) of AEMs is indeed a significant parameter that deter-
mines how well they function in diffusion dialysis. In reality, AEM should prioritize high
ion exchange capacity to improve ion transport sites [23]. IEC is a membrane permeability
parameter that is dependent on the functional groups in the membrane matrix [49,50]. It is
the amount of exchangeable ionic groups (equivalents) available per dry membrane weight.
The traditional Mohr approach was used to measure it [12,51]. To ensure that all charge
sites were transitioned to the Cl− form, the samples of the membrane were stabilized in
1.0 (M) NaCl solution for 2 days. To remove any remaining NaCl, the membranes were
then cleaned thoroughly with deionized water. After that, the membranes were stabilized
for two days with Na2 SO4 solution with a concentration of 0.5 (M). Titration was carried
out with a concentration of 0.05 (M) AgNO3 and K2 CrO4 as an indicator which was used
to predict the quantity of Cl− ions that were released. Furthermore, the membrane’s IEC
(ion-exchange capacity; mmol/g) was determined using the formula, IEC = VC/m, where
m, V, and C signify the membrane’s dry weight, titre volume during titration, and AgNO3
solution concentration, respectively.

2.3.3. Water Uptake, Linear Expansion Ratio, and Fixed Group Concentration
WR (Water uptake) measurements were utilized to explore the membrane’s hydrophilic
nature. To validate the dry weight for the samples of the membrane, they were heated and
dried in an oven and weighed precisely. After that, for 72 h, these membranes were sub-
merged in water at a temperature of 25 ◦ C, and their wet weight was recorded accordingly
after the water from the surface of these membranes was removed using tissue paper. The
WR values were then determined using the mass difference before and after the membranes
were entirely dried [41,52] using the following Equation (1) below; as the relative weight
gained per gram for the dried sample:

WWET − WDRY
WR = × 100% (1)
WDRY

where W DRY and W WET denote the weights of dry and wet membranes, respectively.
The dry and wet length data of membranes at room temperature were used to calculate
the linear expansion ratio (LER). The following equation was used to determine the LER of
prepared AEMs [53,54].

Lw − Ld
LER = × 100% (2)
Ld
where the dry and wet membrane lengths, accordingly, are denoted by Ld and Lw .
According to our prior studies, the fixed group concentration in the membrane was
determined using (WR ) water uptake and (IEC) ion exchange capacity [41,48].
Membranes 2022, 12, 95 7 of 16

2.3.4. Diffusion Dialysis for the Mixture of HCl/FeCl2

Diffusion dialysis was performed by utilizing the framework discussed in our prior
research studies [53,55–58]. The following is a representation of the typical experimental
setup. The tests for the DD were conducted in a two-compartment cell that was segregated
via a membrane that had an effective area of about 5.7 cm2 . All membranes were cautiously
stabilized in the feed solution (1 M HCl + 0.25 M FeCl2 ) for two hours prior to the test,
which stimulated the waste acid solution generated in industrial processes, for example,
metallurgical processes or related products. During the analysis, one compartment of
the cell was loaded with 100 mL feed solution and another one with 100 mL distilled
water. In an effort to minimize the concentration polarization, both sides were intensely
agitated. One hour of diffusion was permitted. Following that, all the solutions, feed,
and permeate were extracted from their respective compartments. Titration carried out
using Na2 CO3 aqueous solution with a concentration of 0.05 mol/L determined the HCl
concentrations on both sides, while titration was performed with KMnO4 aqueous solution
with a concentration of 0.002 mol/L determined the FeCl2 concentration. All of the tests
were carried out at a temperature of 25 ◦ C. Using the formula below, the dialysis coefficients
(U) can be determined [41,48,57]:

M
U= (3)
At∆C
where M refers to the quantity of the component transferred in (mol) whereas A specifies
the effective area of the membrane in (m2 ), t refers to the time (h), and ∆C defines the
logarithm mean concentration in between the two chambers in (mol/m3 ). ∆C is calculated
as below [41,48,57]:

C0f − (C tf − Cdt )
∆C = (4)
ln[C0f /(C tf − Cdt )]

where C0f and C tf indicate the feed concentrations at time 0 and t, respectively, and Cdt is the
dialysate concentration at time t.
The dialysis coefficients UH and UFe can be evaluated using Equations (3) and (4).
The separation factor (S) is calculated as the ratio of the dialysis coefficients (U) of the two
species present in the solution represented in Equation (5) below [41,48,57]:

UH
S= (5)
UFe

3. Results and Discussion

3.1. FTIR and Proton NMR Tests
The successful formation for TMA functionalized BPPO-based porous membranes
is validated through FTIR spectrum analysis. Figure 7 illustrates the FTIR spectra for
pristine BPPO as well as the prepared anion exchange membrane. The stretching vibration
of –CH groups (V and δ) existing inside the pristine BPPO and also the prepared anion
exchange membrane generated the reference band in the range of 1446 cm−1 [41,43,52,57].
The symmetrical and asymmetrical stretching vibrations of C-O have adsorption peaks of
1200 cm−1 and 1306 cm−1 , respectively, whilst phenyl groups have peaks of 1470 cm−1 and
1600 cm−1 . The sharp peak observed in the prepared AEM at 1260 cm−1 reflects the C-N
stretching vibrations, which are missing in the membrane of pristine BPPO. The vibration
for C=C stretching present in the phenyl groups is responsible for the band at 1608 cm−1 ,
while C-O-C stretching is responsible for the peak at 1190 cm−1 . [59]. The bands occurring
at 1446 cm−1 are generated by stretching of –CH groups (V and δ) [43]. The stretching of
C-Br in the BPPO membrane caused the band to appear at 750 cm−1 [54,60]. This band
did not show up in the ATR-FTIR spectra of prepared AEMs after the reaction with TMA.
These findings strongly indicate that the prepared AEMs were successfully synthesized.
 stretching vibrations, which are missing in the membrane of pristine BPPO. The vibration
for C=C stretching present in the phenyl groups is responsible for the band at 1608 cm−1,
while C-O-C stretching is responsible for the peak at 1190 cm−1. [59]. The bands occurring
at 1446 cm−1 are generated by stretching of –CH groups (V and δ) [43]. The stretching of
C-Br in the BPPO membrane caused the band to appear at 750 cm−1 [54,60]. This band did
Membranes 2022, 12, 95 8 of 16
not show up in the ATR-FTIR spectra of prepared AEMs after the reaction with TMA.
These findings strongly indicate that the prepared AEMs were successfully synthesized.

7. The infrared (IR) spectrum

Figure 7. spectrum of
of pristine
pristine BPPO
BPPO and
and M4
M4 membranes.
membranes.

Moreover, proton NMR spectroscopy

spectroscopy was
wasalso
alsoused
usedtotoconfirm
confirmthethesuccessful
successfulfabri-
fab-
rication
cation ofofanion
anionexchange
exchange membranes.
membranes. Figure
Figure 8 depict
8 depict thethe proton
proton NMRNMR spectrums
spectrums of theof
the
purepure
BPPOBPPO
and and fabricated
fabricated anionanion exchange
exchange membrane
membrane M4. the
M4. After After the reaction
reaction with
with trime-
trimethylamine,
thylamine, a newa peak
new peak was observed
was observed at 4.5 at 4.5 ppm,
ppm, whichwhich was absent
was absent in the in the proton
proton NMR
Membranes 2022, 12, 95 NMR spectrum of the pure BPPO. This peak is associated with
spectrum of the pure BPPO. This peak is associated with the -CH2-N bond the -CH -N
2 intobond
the9 into
pre-
of 17
the prepared
pared anion exchange
anion exchange membrane
membrane M4,shows
M4, which whichthe shows the successful
successful quaternization
quaternization reaction
reaction
betweenbetween
BPPO and BPPO and trimethylamine.
trimethylamine.

Figure8.8.Proton
Figure ProtonNMR
NMRspectrums
spectrumsofofBPPO
BPPOand
andprepared
preparedanion
anionexchange
exchangemembrane
membraneM4.
M4.

3.2.
3.2.Morphology
Morphology
The
Themorphology
morphologyofofthethedesigned
designedmembranes
membraneswas wasevaluated
evaluatedusing
usingscanning
scanningelectron
electron
microscopy (SEM). Figure 9 present the SEM micrograph of the designed
microscopy (SEM). Figure 9 present the SEM micrograph of the designed membranes’ membranes’
surface
surfacelayers
layersand
andcross-sections. AllAll
cross-sections. of of
thethe
membranes
membranes examined were
examined werereported to possess
reported to pos-
asess
porous morphology. Membrane morphology was determined by the concentration
a porous morphology. Membrane morphology was determined by the concentration of
TMA found in the polymer matrix. The pore size of membranes M1 to M4 increases
of TMA found in the polymer matrix. The pore size of membranes M1 to M4 increases from
16 µm to 44 µm as the ion exchange group concentration in the polymer matrix increases.
from 16 μm to 44 μm as the ion exchange group concentration in the polymer matrix in-
Figure 9 show the changes in morphologies of the prepared membranes as the amount of
creases. Figure 9 show the changes in morphologies of the prepared membranes as the
TMA in the membrane matrix was enhanced. In the cross-sectional micrographs of the
amount of TMA in the membrane matrix was enhanced. In the cross-sectional micro-
membranes, pores that have finger-like morphology can be observed. Moreover, Figure 9
graphs of the membranes, pores that have finger-like morphology can be observed. More-
clearly show that the presence of finger-like structures in membranes M1 to M4 were
over, Figure 9 clearly show that the presence of finger-like structures in membranes M1
to M4 were increased with the content of amine, which is consistent with our previous
findings [41,61]. This can lower the resistance of ions as they pass within the membranes,
making it useful for the separation of mixtures. As a result, these porous morphologies
may be ideal for acid recovery using the DD process.
 surface layers and cross-sections. All of the membranes examined were reported to pos-
sess a porous morphology. Membrane morphology was determined by the concentration
of TMA found in the polymer matrix. The pore size of membranes M1 to M4 increases
from 16 μm to 44 μm as the ion exchange group concentration in the polymer matrix in-
creases. Figure 9 show the changes in morphologies of the prepared membranes as the
Membranes 2022, 12, 95 amount of TMA in the membrane matrix was enhanced. In the cross-sectional micro- 9 of 16
graphs of the membranes, pores that have finger-like morphology can be observed. More-
over, Figure 9 clearly show that the presence of finger-like structures in membranes M1
to M4 were
increased increased
with withofthe
the content content
amine, of is
which amine, which
consistent is consistent
with with
our previous our previous
findings [41,61].
findings
This [41,61].the
can lower This can lower
resistance the resistance
of ions of ions
as they pass as they
within pass within making
the membranes, the membranes,
it useful
making
for it useful for
the separation of the separation
mixtures. As aof mixtures.
result, theseAs a result,
porous these porous
morphologies may morphologies
be ideal for
may recovery
acid be ideal for acidthe
using recovery using the DD process.
DD process.

Figure 9. SEM micrographs of surface (top) and cross-section (bottom) of the prepared porous mem-
Figure 9. SEM micrographs of surface (top) and cross-section (bottom) of the prepared porous
branes.
membranes.
Membranes 2022, 12, 95 3.3. Thermal 10 of 17
3.3. Thermal Decomposition and Chemical
Decomposition and Chemical Stability
Stability of
of the
the Prepared
Prepared Membranes
Membranes
The thermal decomposition behavior for the formulated membranes M1 to M4 is
evaluated by TGA, as seen in in Figure
Figure 10.10. At medium
medium temperatures, the designed AEMs
thermal desorption of water, thermal deamination,
demonstrate good thermal stability and can withstand andtemperatures
thermal oxidation of200
of up to the ◦°C.
mem-
C. The
brane polymer were the three key stages in the weight loss property
thermal desorption of water, thermal deamination, and thermal oxidation of the membraneof the membranes.
The vaporization
polymer were theofthree
waterkeyfrom the polymer
stages matrixloss
in the weight caused all of of
property thethe
membranes
membranes.to lose
The
weight between
vaporization 90–140from
of water °C during the first
the polymer step.
matrix At 250
caused all °C, themembranes
of the quaternarytoammonium
lose weight
group
between 90–140 ◦ Cculminating
deteriorated, during the in thestep.
first second 250 ◦ C,loss
At weight the stage [54]. The
quaternary cleavage of
ammonium the
group
main polymer matrix is responsible for the final stage of weight loss, which
deteriorated, culminating in the second weight loss stage [54]. The cleavage of the main occurred at
420 °C.
polymer matrix is responsible for the final stage of weight loss, which occurred at 420 C. ◦

Figure
Figure10.
10.Thermal gravimetric
Thermal analysis
gravimetric (TGA)
analysis thermograms
(TGA) for various
thermograms porousporous
for various BPPO-based mem-
BPPO-based
branes.
membranes.

Figure 11 demonstrate the chemical stability of the designed AEMs after two weeks
at ambient temperature immersion in 2 M concentration of HCl. Here, the weight loss of
the membrane after immersion in a 2 M HCl solution at room temperature is referred to
as chemical stability. After two weeks of immersion in the 2 M HCl solution, all of the
Membranes 2022, 12, 95 10 of 16

Figure 11 demonstrate the chemical stability of the designed AEMs after two weeks
at ambient temperature immersion in 2 M concentration of HCl. Here, the weight loss of
the membrane after immersion in a 2 M HCl solution at room temperature is referred to
as chemical stability. After two weeks of immersion in the 2 M HCl solution, all of the
prepared membranes demonstrated good chemical stability, while their color remained
unchanged. The weight loss (%) of the prepared membranes ranged from 11.90% to
15.38%, with membranes comprising the most TMA indicated the maximum weight loss.
Furthermore, by increasing the amount of TMA in the polymer matrix, weight loss was
increased substantially from M1 to M4. Thus, with a two-week immersion, the maximum
Membranes 2022, 12, 95 11 of 17
weight loss was just around 15.38%. This indicated that the AEMs that have been prepared
are incredibly effective in terms of DD application for acid recovery.

Figure 11. Chemical

Figure 11. Chemical stability
stability of
of membrane
membrane M1
M1 to
to M4
M4 after
after immersion
immersion in
in 22 M
M HCl
HCl for
for two
two weeks
weeks at
at
room
room temperature.
temperature.

3.4. Ion Exchange Capacity (IEC) and Fixed Group Concentration (CR )
3.4. Ion Exchange Capacity (IEC) and Fixed Group Concentration (CR)
A critical variable of AEMs used for the DD process is the ion exchange capacity they
A critical variable of AEMs used for the DD process is the ion exchange capacity they
have. Hence, this variable was measured by the classical Mohr’s method and depicted
have. Hence, this variable was measured by the classical Mohr’s method and depicted in
in Table 1. The value of IEC was reported in the range of 0.71 mmol/g to 1.43 mmol/g.
Table 1. The value of IEC was reported in the range of 0.71 mmol/g to 1.43 mmol/g. In
In other words, it was observed that as the concentration of TMA in the polymer matrix
other words, it was observed that as the concentration of TMA in the polymer matrix in-
increased, the IEC also enhanced from 0.71 mmol/g to 1.43 mmol/g.
creased, the IEC also enhanced from 0.71 mmol/g to 1.43 mmol/g.
Fixed group concentration (CR ) was typically determined by dividing the IEC (ion
Fixedcapacity)
exchange group concentration
with the WR (water(CR) was typically
uptake). determined
According by dividing
to previous the IEC
researchers, it is(ion
an
exchangeparameter
essential capacity) with the Wand
of AEMs, R (water uptake). According to previous researchers, it is an
variations in CR values can have a significant impact on
essential
the parameter of
DD performance of AEMs, and variations
the membrane [41,48]. in
AtCambient
R values can have a significant impact on
temperature, the CR (fixed group
concentration) of the formulated membranes wasAt
the DD performance of the membrane [41,48]. ambientand
evaluated, temperature,
the results the CR (fixed
obtained are
group concentration) of the formulated membranes was evaluated, and
presented in Table 1. It was discovered that as the concentration of TMA in the polymer the results ob-
matrix increased, the fixed group concentration (CR ) also surged from 0.0047 mol/Lthe
tained are presented in Table 1. It was discovered that as the concentration of TMA in to
polymer
0.0056 matrix increased, the fixed group concentration (CR) also surged from 0.0047
mol/L.
mol/L to 0.0056 mol/L.
3.5. Water Uptake and Linear Expansion Ratio
3.5. Water
IEM’sUptake and Linear
water uptake (W Expansion
) is a usefulRatio
tool that has a measurable impact on the phenom-
R
ena ofIEM’s water uptake
separation, as well as(Wthe
R) is a useful tool
dimensional that
and has a measurable
mechanical impact[41,52,62–64].
characteristics on the phe-
nomena
Water of separation,
molecules existing inasthewell as the matrix
membrane dimensional and mechanical
will facilitate the separationcharacteristics
of charged
[41,52,62–64].
functional Water
groups, molecules
which existing
is essential for in
ionthe membrane
transport matrix
[52,64]. As will facilitate
presented the separa-
in Table 1, the
W
tion(water uptake) of the prepared membranes enhanced from 149.60% to 233.80%
R of charged functional groups, which is essential for ion transport [52,64]. As presented as the
concentration
in Table 1, theofWTMA in the
R (water membrane
uptake) matrix increased.
of the prepared membranes Capillary tension
enhanced fromis149.60%
primarily to
responsible for concentration
233.80% as the its association ofwith
TMAtheinporous structure.matrix
the membrane From increased.
this perspective,
Capillarythe tension
porous
is primarily responsible for its association with the porous structure. From this perspec-
tive, the porous AEMs should possess marginally greater water uptake than dense AEMs
whenever the ion exchange capacities are equivalent [41].
IEMs have a significant factor called the linear expansion ratio (LER). Membranes
Membranes 2022, 12, 95 11 of 16

AEMs should possess marginally greater water uptake than dense AEMs whenever the ion
exchange capacities are equivalent [41].
IEMs have a significant factor called the linear expansion ratio (LER). Membranes with
a high LER exhibited poor durability and mechanical stability, thereby reducing membrane
performance. Table 1 show the findings of the investigation performed at room temperature.
It was discovered that increasing the concentration of TMA in the polymer matrix increased
the (LER) ratio from 3.88% to 9.23%. Furthermore, both water uptake and swelling behavior
were influenced by the hydrophilic nature of the membrane matrix as well as the degree of
plasticization [65]. The durability of the polymeric matrix ensures an increase in swelling
Membranes 2022, 12, 95 12 of 17
ratio as well as the water uptake at a lower degree of plasticization (i.e., the inclusion of
high hydrophilic sites), which is aimed at improving the acid recovery performance [66,67].
(i.e., the inclusion of high hydrophilic sites), which is aimed at improving the acid recov-
3.6.
ery Water Contact
performance Angle
[66,67].
One of the essential features of ion-exchange membranes is the water contact angle
3.6. Water Contact Angle
which is used to determine their hydrophilicity. At ambient temperature, the water contact
One of the essential features of ion-exchange membranes is the water contact angle
angle
whichof prepared
is used membranes
to determine M1 to M4Atwas
their hydrophilicity. determined,
ambient temperature,and the results
the water con- are shown in
Figure 12a,b.
tact angle The water
of prepared contact
membranes M1 toangle
M4 was for the formulated
determined, membranes
and the results are shownwas observed to
be
in lowered from
Figure 12a,b. membranes
The water M1 for
contact angle to the
M4formulated
as the concentration
membranes was of TMA toin the membrane
observed
be lowered
matrix from membranes
increases, as per theseM1 to M4 as the
figures. Thisconcentration
is related of
to TMA in the membrane
the enhancement in the hydrophilic
matrix increases, as per these figures. This is related to the enhancement in the hydrophilic
nature of membranes as the ion exchange contents in the polymer
nature of membranes as the ion exchange contents in the polymer matrix increased. For
matrix increased. For
DD
DDapplications,
applications, thethe increased
increased hydrophilicity
hydrophilicity of preparedof membranes
prepared ismembranes
favorable. is favorable.

(a)

(b)
Figure 12. (a): water contact angle of membranes M1 to M4; (b): Water contact images of membranes
Figure 12. (a): water contact angle of membranes M1 to M4; (b): Water contact images of membranes
M1 to M4.
M1 to M4.
 Membranes 2022, 12, 95 13 of 17
Membranes 2022, 12, 95 12 of 16

3.7. DD for HCl/FeCl2 Solution

3.7. DD Theforacid
HCl/FeCl 2 Solution
dialysis coefficient (UH) and acid/salt separation factor (S) of AEMs are em-
ployed to directly assess
The acid dialysis coefficient the ability (UHof) and
recovery and purity
acid/salt for the
separation acid (S)
factor thatofisAEMs
recovered;
are
these are the essential factors to evaluate DD efficiency. Nevertheless,
employed to directly assess the ability of recovery and purity for the acid that is recovered; certain commercial
AEMs
these arehave low acid factors
the essential recovery to ability
evaluate during the DD process,
DD efficiency. which certain
Nevertheless, restrictscommercial
their use in
acid recovery
AEMs have lowapplications.
acid recovery Due to theduring
ability extreme thepractical
DD process,implementation
which restricts of AEMs in DD,
their use in
the developed
acid AEMs with Due
recovery applications. better toacid dialysis coefficients
the extreme must be designed
practical implementation basedinonDD,
of AEMs the
structure–performance
the developed AEMs with relationship
better acidofdialysis membrane materials
coefficients must [23].
be designed based on the
After the in-depthrelationship
structure–performance analysis andofcomprehensive
membrane materials characterizations
[23]. of the prepared po-
rousAfter the in-depth
membranes, analysis was
an experiment and conducted
comprehensive in thischaracterizations
study using an HCl of+the
FeClprepared
2 mixture

porous membranes, an
with concentrations experiment
of 0.1M HCl and was conducted
0.25M FeCl2 for in exploring
this studypossible
using an HCl + FeClfor
applications 2
mixture with concentrations
the membrane applications of 0.1 Mrecovery
in acid HCl andthrough 0.25 M FeCl 2 for exploring
diffusion possible
dialysis process. applica-
According
tions
to theforobtained
the membrane applications
DD results, it was found in acid recovery
that through
the dialysis diffusion
coefficient of dialysis
HCl (UHprocess.
) for the
According
prepared to the obtained
membranes DD results,
ranges from 0.0043 it wasm/h found that the
to 0.012 m/h dialysis
at room coefficient of HClas(Upre-
temperature, H)
for the prepared membranes ranges from 0.0043 m/h to 0.012
sented in Figure 13. It was also discovered that as the concentration of TMA in the polymerm/h at room temperature,
asmatrix
presented in Figure
increased, 13. It was
the values of U also discovered
H gradually that as from
increased the concentration
membranes M1 of TMA
to M4.in As
thea
polymer matrixon
result, based increased, the values offindings,
the aforementioned UH gradually increasedreferences
two separate from membranesmay beM1 to M4.
obtained.
As a result, based
Primarily, on the aforementioned
the recorded UH values are relatively findings, larger
two separate
than those references may be obtained.
of commercial DF-120B
Primarily,
membrane the recorded
with UH value UH ofvalues
0.004are m/h. relatively
Secondly, larger than
these those
values ofnearly
are commercial DF-120B
identical to our
membrane U
formerly published membranes with UH around 0.010 m/h at a temperature of 25 °C our
with H value of 0.004 m/h. Secondly, these values are nearly identical to [41].
formerly
The porous published
structuremembranes
and growth with in UtheH around 0.010 m/h
ion-exchange group at inside
a temperature of 25 ◦ Cmatrix
the membrane [41].
The
mayporous
indeedstructure and growth
be primarily responsible in the forion-exchange group inside
the steady increase the membrane
in UH values. The active matrix
zone,
may indeed be primarily responsible for the steady
also known as the ion-exchange party, is present in all the prepared increase in U H values. The active
porous membranes zone,
also
andknown as the ion-exchange
is responsible for ion transfer party,
acrossis present in all the As
the membrane. prepared porous
the amount ofmembranes
TMA in the
and is responsible
polymer matrix was for gradually
ion transfer across the
increased from membrane.
membraneAs M1thetoamount
M4, theof TMA
IEC andinWthe R of
polymer matrix was gradually increased from membrane
the membranes also increased, resulting in enhanced hydrophilicity of membranes M1 to M4, the IEC and W R of the
and
membranes
higher UH valuesalso increased, resultingmembranes.
of the prepared in enhancedThe hydrophilicity
presence of of themembranes
–N+(CH3)3Br and higherin
− group
UH values of the prepared membranes. −The presence of the –N+ (CH3 )3+Br− group in the
the membranes significantly enabled Cl ions to move through them. H ions can also pass
membranes significantly enabled Cl− ions to move through them. H+ ions can also pass
across the membranes with Cl − to achieve electrical neutrality [68]. Fe-related components
across the membranes with Cl− to achieve electrical neutrality [68]. Fe-related components
such as Fe 2+ and FeCl+, on the other hand, are less likely to move through the membrane
such as Fe2+ and FeCl+ , on the other hand, are less likely to move through the membrane
due to their greater size and reduced mobility [67,68].
due to their greater size and reduced mobility [67,68].

Figure13.
Figure 13.Acid
Aciddialysis
dialysiscoefficient
coefficient(U
(U H) at 25◦ °C for different representative porous BPPO-based
H ) at 25 C for different representative porous BPPO-based
membranes.
membranes.

Figure14
Figure 14 depict
depict the values
valuesof
ofseparation
separationfactor
factor(S)(S)
asas
a ratio of U
a ratio ofH to
UHUto
Fe. The
UFe .S The
values
S
acquired
values for thefor
acquired prepared membrane
the prepared M1 toM1
membrane M4 torange
M4 rangefromfrom
13.1413.14
to 32.87, implying
to 32.87, that
implying
that the S value for the prepared membrane M4 is almost identical to that of PVA-based
Membranes 2022, 12, 95 14 of 17

Membranes 2022, 12, 95 13 of 16

the S value for the prepared membrane M4 is almost identical to that of PVA-based hybrid
membranes (22–39) at 25 °C [63],◦(12.1–35.7) at 25 °C [43],◦ and (18.5–21) at 25 °C [69]. Pre-
hybrid membranes (22–39) at 25 C [63], (12.1–35.7) at 25 C [43], and (18.5–21) at 25 ◦ C [69].
vious studies have indicated that the separation factor is influenced by the structure of the
Previous studies have indicated that the separation factor is influenced by the structure of
membrane and its functional groups. This study indicated that as the amount of TMA in
the membrane and its functional groups. This study indicated that as the amount of TMA
the prepared membranes M1 to M4 increases, the IEC values gradually increase and that
in the prepared membranes M1 to M4 increases, the IEC values gradually increase and that
this increased IEC is effective in finding a high S value. Furthermore, as shown by the
this increased IEC is effective in finding a high S value. Furthermore, as shown by the SEM
SEM micrographs in Figure 9, the prepared membranes M1 to M4 contain porous mor-
micrographs in Figure 9, the prepared membranes M1 to M4 contain porous morphologies.
phologies. During the ion transport process, the resistance was reduced by the porous
During the ion transport process, the resistance was reduced by the porous morphology.
morphology. Because the membrane structure+ is porous, H+ ions can transfer easily, in-
Because the membrane structure is porous, H ions can transfer easily, increasing the UH
creasing the UH value; however, smaller pore sizes can greatly impede the transport of
value; however, smaller pore sizes can greatly impede the transport of FeCl2 , increasing
FeCl
the S2, increasing the S values. Hence, from the prepared membranes M1 to M4, we see a
values. Hence, from the prepared membranes M1 to M4, we see a rising trend in S
rising
values.trend in S values.
The prepared Themembranes
porous prepared porous membranes
M1 to M4 M1 to M4
can be effectively can
used forbeacid
effectively
recovery
used for acid recovery through diffusion dialysis process from the perspective
through diffusion dialysis process from the perspective of acid dialysis coefficient of acid and
di-
alysis coefficient
separation factor. and separation factor.

Figure
Figure14.
14. Separation Factoratat2525◦ C°Cforfor
Separation Factor multiple
multiple representatives
representatives for porous
for porous BPPO-based
BPPO-based mem-
membranes.
branes.
4. Conclusions
Porous BPPO-based AEMs were developed using a phase-inversion technique in
4. Conclusions
ethanol medium
Porous in this manuscript.
BPPO-based AEMs were Thedeveloped
trimethylammonium group in the prepared
using a phase-inversion AEMs
technique in
was responsible for Cl − transfer within the polymer matrix. FTIR and proton NMR tests
ethanol medium in this manuscript. The trimethylammonium group in the prepared
verified
AEMs theresponsible
was reaction between
for Cl−BPPO andwithin
transfer TMA. The thermal and
the polymer acid FTIR
matrix. stability
andofproton
the prepared
NMR
membranes were exceptional. Additionally, the prepared membranes
tests verified the reaction between BPPO and TMA. The thermal and acid stabilitywere proven to of
have
thea
higher W (water uptake), IEC (ion exchange capacity),
prepared Rmembranes were exceptional. Additionally, the preparedand C R (fixed group concentration).
membranes were
proven to have a higher WR (water uptake), IEC (ion exchangedemonstrated
The increased hydrophilicity of the developed membranes was capacity), andbyCthe(fixed
R
water
contact angle. The DD process for the recovery of acid was used to investigate the separation
group concentration). The increased hydrophilicity of the developed membranes was
efficiency of the prepared membranes at ambient temperature. The observations led to a
demonstrated by the water contact angle. The DD process for the recovery of acid was
higher dialysis coefficient of acid (HCl) (0.0034–0.012 m/h) and a higher separation factor
used to investigate the separation efficiency of the prepared membranes at ambient tem-
(S) (13.14–32.87). Therefore, diffusion dialysis can be potentially applied to recover acid
perature. The observations led to a higher dialysis coefficient of acid (HCl) (0.0034–0.012
using these formulated porous BPPO-based anion exchange membranes.
m/h) and a higher separation factor (S) (13.14–32.87). Therefore, diffusion dialysis can be
potentially applied to recover acid using these formulated porous BPPO-based anion ex-
Author Contributions: Conceptualization, M.I.K., M.K., A.S. and F.A.; methodology, M.I.K. and M.K.;
change membranes.
software, F.A.; validation, all authors.; formal analysis, M.I.K. writing—original draft preparation
M.I.K. and M.K. writing—review and editing, F.A. All authors have read and agreed to the published
Author
version Contributions: Conceptualization, M.I.K., M.K., A.S. and F.A.; methodology, M.I.K. and
of the manuscript.
M.K.; software, F.A.; validation, all authors.; formal analysis, M.I.K. writing—original draft prepa-
Funding:
ration Qatar
M.I.K. andUniversity grant QUCG-CENG-21/22-4.
M. K. writing—review and editing, F.A. All authors have read and agreed to the
published version of the manuscript.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Membranes 2022, 12, 95 14 of 16

Data Availability Statement: Not applicable.

Acknowledgments: The contents herein are solely the responsibility of the authors. In addition, the
work was made possible by an Internal Qatar University grant QUCG-CENG-21/22-4.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations

AEM Anion exchange membrane

BPPO Brominated poly(2,6-dimethyl-1,4-phenylene oxide)
CR Fixed group concentration
DD Diffusion dialysis
IEC Ion exchange capacity
IEM Ion exchange membrane
NMP N-Methyl-2-pyrrolidone
SEM Scanning electron microscopy
S Separation factor
TGA Thermogravimetric analysis
TMA Trimethylamine
UH Diffusion dialysis coefficient of HCl
UFe Diffusion dialysis coefficient of FeCl2
WR Water uptake

References
1. Xu, T.; Yang, W. Industrial recovery of mixed acid (HF+HNO3 ) from the titanium spent leaching solutions by diffusion dialysis
with a new series of anion exchange membranes. J. Membr. Sci. 2003, 220, 89–95. [CrossRef]
2. Agrawal, A.; Sahu, K.K. An overview of the recovery of acid from spent acidic solutions from steel and electroplating industries.
J. Hazard. Mater. 2009, 171, 61–75. [CrossRef] [PubMed]
3. Gueccia, R.; Randazzo, S.; Chillura Martino, D.; Cipollina, A.; Micale, G. Experimental investigation and modeling of diffusion
dialysis for hcl recovery from waste pickling solution. J. Environ. Manag. 2019, 235, 202–212. [CrossRef]
4. Wang, Y.; Chen, F.; Ma, X.; Zhang, G. Recovery of nitric and acetic acids from etching waste solutions using a synergistic system
consisting of n235 and trpo in cyclohexane. Hydrometallurgy 2019, 185, 23–29. [CrossRef]
5. Chen, F.; Wang, X.; Liu, W.; Liang, B.; Yue, H.; Li, C. Selective extraction of nitric and acetic acids from etching waste acid using
n235 and mibk mixtures. Sep. Purif. Technol. 2016, 169, 50–58. [CrossRef]
6. Narěbska, A.; Staniszewski, M. Separation of fermentation products by membrane techniques. I. Separation of lactic acid/lactates
by diffusion dialysis. Sep. Sci. Technol. 1997, 32, 1669–1682. [CrossRef]
7. Palatý, Z.; Stoček, P.; Bendová, H.; Prchal, P. Continuous dialysis of carboxylic acids: Solubility and diffusivity in neosepta-amh
membranes. Desalination 2009, 243, 65–73. [CrossRef]
8. Luo, J.; Wu, C.; Xu, T.; Wu, Y. Diffusion dialysis-concept, principle and applications. J. Membr. Sci. 2011, 366, 1–16. [CrossRef]
9. Lie, H.; Ming, C.; Xiong-jiao, Z. Acid waste water comprehensive treatment rebuilding engineering practice. Metal Products 2009,
1, 020.
10. Lei, Q.; He, D.; Zhou, K.; Zhang, X.; Peng, C.; Chen, W. Separation and recovery of scandium and titanium from red mud leaching
liquor through a neutralization precipitation-acid leaching approach. J. Rare Earths 2020, 39, 1126–1132. [CrossRef]
11. Ni, C.; Wu, X.; Dan, J.; Du, D. Facile recovery of acetic acid from waste acids of electronic industry via a partial neutralization
pretreatment (pnp)–distillation strategy. Sep. Purif. Technol. 2014, 132, 23–26. [CrossRef]
12. Khan, M.I.; Shanableh, A.; Elboughdiri, N.; Kriaa, K.; Ghernaout, D.; Ghareba, S.; Khraisheh, M.; Lashari, M.H. Higher acid
recovery efficiency of novel functionalized inorganic/organic composite anion exchange membranes from acidic wastewater.
Membranes 2021, 11, 133. [CrossRef]
13. Shin, C.-H.; Kim, J.-Y.; Kim, J.-Y.; Kim, H.-S.; Lee, H.-S.; Mohapatra, D.; Ahn, J.-W.; Ahn, J.-G.; Bae, W. Recovery of nitric acid from
waste etching solution using solvent extraction. J. Hazard. Mater. 2009, 163, 729–734. [CrossRef]
14. Ahmad, A.; Othman, I.; Taher, H.; Banat, F. Lactic acid recovery from date pulp waste fermentation broth by ions exchange resins.
Environ. Technol. Innov. 2021, 22, 101438. [CrossRef]
15. Yan, R.; Luo, D.; Fu, C.; Wang, Y.; Zhang, H.; Wu, P.; Jiang, W. Harmless treatment and selective recovery of acidic Cu(II)-Cr(VI)
hybrid wastewater via coupled photo-reduction and ion exchange. Sep. Purif. Technol. 2020, 234, 116130. [CrossRef]
16. Chen, K.; Hao, S.; Lyu, H.; Luo, G.; Zhang, S.; Chen, J. Ion exchange separation for recovery of monosaccharides, organic acids
and phenolic compounds from hydrolysates of lignocellulosic biomass. Sep. Purif. Technol. 2017, 172, 100–106. [CrossRef]
17. Zhang, K.; Yang, S.-T. In situ recovery of fumaric acid by intermittent adsorption with ira-900 ion exchange resin for enhanced
fumaric acid production by rhizopus oryzae. Biochem. Eng. J. 2015, 96, 38–45. [CrossRef]
Membranes 2022, 12, 95 15 of 16

18. Lin, S.H.; Kiang, C.D. Chromic acid recovery from waste acid solution by an ion exchange process: Equilibrium and column ion
exchange modeling. Chem. Eng. J. 2003, 92, 193–199. [CrossRef]
19. Choi, J.-H.; Kim, S.-H.; Moon, S.-H. Recovery of lactic acid from sodium lactate by ion substitution using ion-exchange membrane.
Sep. Purif. Technol. 2002, 28, 69–79. [CrossRef]
20. Khan, M.I.; Khraisheh, M. Synthesis and characterization of stable anion exchange membranes for desalination applications.
Desalin. Water Treat. 2018, 113, 36–44. [CrossRef]
21. Xu, T. Ion exchange membranes: State of their development and perspective. J. Membr. Sci. 2005, 263, 1–29. [CrossRef]
22. Afsar, N.U.; Erigene, B.; Irfan, M.; Wu, B.; Xu, T.; Ji, W.; Emmanuel, K.; Ge, L.; Xu, T. High performance anion exchange membrane
with proton transport pathways for diffusion dialysis. Sep. Purif. Technol. 2018, 193, 11–20. [CrossRef]
23. Lin, J.; Huang, J.; Wang, J.; Yu, J.; You, X.; Lin, X.; Van der Bruggen, B.; Zhao, S. High-performance porous anion exchange
membranes for efficient acid recovery from acidic wastewater by diffusion dialysis. J. Membr. Sci. 2021, 624, 119116. [CrossRef]
24. Merkel, A.; Čopák, L.; Dvořák, L.; Golubenko, D.; Šeda, L. Recovery of spent sulphuric acid by diffusion dialysis using a spiral
wound module. Int. J. Mol. Sci. 2021, 22, 11819. [CrossRef] [PubMed]
25. Wei, C.; Li, X.; Deng, Z.; Fan, G.; Li, M.; Li, C. Recovery of H2 SO4 from an acid leach solution by diffusion dialysis. J. Hazard.
Mater. 2010, 176, 226–230. [CrossRef]
26. Emmanuel, K.; Cheng, C.; Mondal, A.N.; Erigene, B.; Hossain, M.M.; Afsar, N.U.; Khan, M.I.; Wu, L.; Xu, T. Covalently cross-
linked pyridinium based aems with aromatic pendant groups for acid recovery via diffusion dialysis. Sep. Purif. Technol. 2016,
164, 125–131. [CrossRef]
27. Sharma, J.; Misra, S.K.; Kulshrestha, V. Internally cross-linked poly(2,6-dimethyl-1,4-phenylene ether) based anion exchange
membrane for recovery of different acids by diffusion dialysis. Chem. Eng. J. 2021, 414, 128776. [CrossRef]
28. Yadav, V.; Raj, S.K.; Rathod, N.H.; Kulshrestha, V. Polysulfone/graphene quantum dots composite anion exchange membrane for
acid recovery by diffusion dialysis. J. Membr. Sci. 2020, 611, 118331. [CrossRef]
29. Irfan, M.; Afsar, N.U.; Wang, Y.; Xu, T. Investigation of key process parameters in acid recovery for diffusion dialysis using novel
(MDMH-QPPO) anion exchange membranes. J. Taiwan Inst. Chem. Eng. 2018, 93, 405–413. [CrossRef]
30. Irfan, M.; Bakangura, E.; Afsar, N.U.; Xu, T. Augmenting acid recovery from different systems by novel q-dan anion exchange
membranes via diffusion dialysis. Sep. Purif. Technol. 2018, 201, 336–345. [CrossRef]
31. Mondal, A.N.; Cheng, C.; Khan, M.I.; Hossain, M.M.; Emmanuel, K.; Ge, L.; Wu, B.; He, Y.; Ran, J.; Ge, X.; et al. Improved acid
recovery performance by novel poly(dmaem-co-γ-mps) anion exchange membrane via diffusion dialysis. J. Membr. Sci. 2017, 525,
163–174. [CrossRef]
32. Zhang, C.; Zhang, W.; Wang, Y. Diffusion dialysis for acid recovery from acidic waste solutions: Anion exchange membranes and
technology integration. Membranes 2020, 10, 169. [CrossRef] [PubMed]
33. Xue, S.; Wu, C.; Wu, Y.; Zhang, C. An optimized process for treating sodium acetate waste residue: Coupling of diffusion dialysis
or electrodialysis with bipolar membrane electrodialysis. Chem. Eng. Res. Des. 2018, 129, 237–247. [CrossRef]
34. Ruiz-Aguirre, A.; Lopez, J.; Gueccia, R.; Randazzo, S.; Cipollina, A.; Cortina, J.L.; Micale, G. Diffusion dialysis for the treatment of
H2 SO4 -CuSO4 solutions from electroplating plants: Ions membrane transport characterization and modelling. Sep. Purif. Technol.
2021, 266, 118215. [CrossRef]
35. Wang, L.; Zhang, F.; Li, Z.; Liao, J.; Huang, Y.; Lei, Y.; Li, N. Mixed-charge poly(2,6-dimethyl-phenylene oxide) anion exchange
membrane for diffusion dialysis in acid recovery. J. Membr. Sci. 2018, 549, 543–549. [CrossRef]
36. Lin, X.; Shamsaei, E.; Kong, B.; Liu, J.Z.; Hu, Y.; Xu, T.; Wang, H. Porous diffusion dialysis membranes for rapid acid recovery. J.
Membr. Sci. 2016, 502, 76–83. [CrossRef]
37. Stachera, D.M.; Childs, R.F. Tuning the acid recovery performance of poly(4-vinylpyridine)-filled membranes by the introduction
of hydrophobic groups. J. Membr. Sci. 2001, 187, 213–225. [CrossRef]
38. Pandey, A.K.; Childs, R.F.; West, M.; Lott, J.N.; McCarry, B.E.; Dickson, J.M. Formation of pore-filled ion-exchange membranes
with in situ crosslinking: poly(vinylbenzyl ammonium salt)-filled membranes. J. Polym. Sci. Part A Polym. Chem. 2001, 39,
807–820. [CrossRef]
39. Stachera, D.M.; Childs, R.F.; Mika, A.M.; Dickson, J.M. Acid recovery using diffusion dialysis with poly(4-vinylpyridine)-filled
microporous membranes. J. Membr. Sci. 1998, 148, 119–127. [CrossRef]
40. Kim, D.-H.; Park, J.-H.; Seo, S.-J.; Park, J.-S.; Jung, S.; Kang, Y.S.; Choi, J.-H.; Kang, M.-S. Development of thin anion-exchange
pore-filled membranes for high diffusion dialysis performance. J. Membr. Sci. 2013, 447, 80–86. [CrossRef]
41. Khan, M.I.; Mondal, A.N.; Cheng, C.; Pan, C.; Emmanuel, K.; Wu, L.; Xu, T. Porous BPPO-based membranes modified by aromatic
amine for acid recovery. Sep. Purif. Technol. 2016, 157, 27–34. [CrossRef]
42. Wu, Y.; Luo, J.; Wu, C.; Xu, T.; Fu, Y. Bionic multisilicon copolymers used as novel cross-linking agents for preparing anion
exchange hybrid membranes. J. Phys. Chem. B 2011, 115, 6474–6483. [CrossRef] [PubMed]
43. Wu, C.; Wu, Y.; Luo, J.; Xu, T.; Fu, Y. Anion exchange hybrid membranes from pva and multi-alkoxy silicon copolymer tailored
for diffusion dialysis process. J. Membr. Sci. 2010, 356, 96–104. [CrossRef]
44. Wu, Y.; Wu, C.; Li, Y.; Xu, T.; Fu, Y. PVA–silica anion-exchange hybrid membranes prepared through a copolymer crosslinking
agent. J. Membr. Sci. 2010, 350, 322–332. [CrossRef]
45. Klaysom, C.; Moon, S.-H.; Ladewig, B.P.; Lu, G.Q.M.; Wang, L. Preparation of porous ion-exchange membranes (iems) and their
characterizations. J. Membr. Sci. 2011, 371, 37–44. [CrossRef]
Membranes 2022, 12, 95 16 of 16

46. Klaysom, C.; Marschall, R.; Moon, S.-H.; Ladewig, B.P.; Lu, G.Q.M.; Wang, L. Preparation of porous composite ion-exchange
membranes for desalination application. J. Mater. Chem. 2011, 21, 7401–7409. [CrossRef]
47. Sun, F.; Wu, C.; Wu, Y.; Xu, T. Porous BPPO-based membranes modified by multisilicon copolymer for application in diffusion
dialysis. J. Membr. Sci. 2014, 450, 103–110. [CrossRef]
48. Khan, M.I.; Wu, L.; Hossain, M.M.; Pan, J.; Ran, J.; Mondal, A.N.; Xu, T. Preparation of diffusion dialysis membrane for acid
recovery via a phase-inversion method. Membr. Water Treat. 2015, 6, 365–378. [CrossRef]
49. Zhang, Z.; Wu, L.; Varcoe, J.; Li, C.; Ong, A.L.; Poynton, S.; Xu, T. Aromatic polyelectrolytes via polyacylation of pre-quaternized
monomers for alkaline fuel cells. J. Mater. Chem. A 2013, 1, 2595–2601. [CrossRef]
50. Yue, X.; Wu, W.; Chen, G.; Yang, C.; Liao, S.; Li, X. Influence of 2,20 ,6,60 -tetramethyl biphenol-based anion-exchange membranes
on the diffusion dialysis of hydrochloride acid. J. Appl. Polym. Sci. 2017, 134, 45333. [CrossRef]
51. Khan, M.I.; Li, X.; Fernandez-Garcia, J.; Lashari, M.H.; Rehman, A.; Elboughdiri, N.; Kolsi, L.; Ghernaout, D. Effect of different
quaternary ammonium groups on the hydroxide conductivity and stability of anion exchange membranes. ACS Omega 2021, 6,
7994–8001. [CrossRef] [PubMed]
52. Khan, M.I.; Mondal, A.N.; Tong, B.; Jiang, C.; Emmanuel, K.; Yang, Z.; Wu, L.; Xu, T. Development of BPPO-based anion exchange
membranes for electrodialysis desalination applications. Desalination 2016, 391, 61–68. [CrossRef]
53. Khan, M.I.; Su, J.; Guo, L. Preparation and characterization of high-performance anion exchange membranes for acid recovery.
Desal. Water Treat. 2021, 209, 144–154. [CrossRef]
54. Khan, M.I.; Zheng, C.; Mondal, A.N.; Hossain, M.M.; Wu, B.; Emmanuel, K.; Wu, L.; Xu, T. Preparation of anion exchange
membranes from bppo and dimethylethanolamine for electrodialysis. Desalination 2017, 402, 10–18. [CrossRef]
55. Khan, M.I.; Luque, R.; Prinsen, P.; Rehman, A.; Anjum, S.; Nawaz, M.; Shaheen, A.; Zafar, S.; Mustaqeem, M. BPPO-based anion
exchange membranes for acid recovery via diffusion dialysis. Materials 2017, 10, 266. [CrossRef]
56. Khan, M.I.; Su, J.; Lichtfouse, E.; Guo, L. Higher efficiency of triethanolamine-grafted anion exchange membranes for acidic
wastewater treatment. Desal. Water Treat. 2020, 197, 41–51. [CrossRef]
57. Khan, M.I.; Mondal, A.N.; Emmanuel, K.; Hossain, M.M.; Afsar, N.U.; Wu, L.; Xu, T. Preparation of pyrrolidinium-based
anion-exchange membranes for acid recovery via diffusion dialysis. Sep. Sci. Technol. 2016, 51, 1881–1890. [CrossRef]
58. Khan, M.I.; Khraisheh, M.; Almomani, F. Fabrication and characterization of pyridinium functionalized anion exchange mem-
branes for acid recovery. Sci. Total Environ. 2019, 686, 90–96. [CrossRef]
59. Yang, W.; Wu, C.; Gong, M.; Xu, T. New anion exchanger organic–inorganic hybrids and membranes from a copolymer of
glycidylmethacrylate and -methacryloxypropyl trimethoxy silane. J. Appl. Polym. Sci. 2006, 102, 3580–3589.
60. Arges, C.G.; Wang, L.; Jung, M.-S.; Ramani, V. Mechanically stable poly(arylene ether) anion exchange membranes prepared from
commercially available polymers for alkaline electrochemical devices. J. Electrochem. Soc. 2015, 162, F686–F693. [CrossRef]
61. Tang, B.; Xu, T.; Gong, M.; Yang, W. A novel positively charged asymmetry membranes from poly(2,6-dimethyl-1,4-phenylene
oxide) by benzyl bromination and in situ amination: Membrane preparation and characterization. J. Membr. Sci. 2005, 248,
119–125. [CrossRef]
62. Spry, D.B.; Goun, A.; Glusac, K.; Moilanen, D.E.; Fayer, M.D. Proton transport and the water environment in nafion fuel cell
membranes and aot reverse micelles. J. Am. Chem. Soc. 2007, 129, 8122–8130. [CrossRef] [PubMed]
63. Wang, C.; Wu, C.; Wu, Y.; Gu, J.; Xu, T. Polyelectrolyte complex/PVA membranes for diffusion dialysis. J. Hazard. Mater. 2013,
261, 114–122. [CrossRef]
64. Chakrabarty, T.; Singh, A.K.; Shahi, V.K. Zwitterionic silica copolymer based crosslinked organic-inorganic hybrid polymer
electrolyte membranes for fuel cell applications. RSC Adv. 2012, 2, 1949–1961. [CrossRef]
65. Mangiagli, P.; Ewing, C.; Xu, K.; Wang, Q.; Hickner, M. Dynamic water uptake of flexible ion-containing polymer networks. Fuel
Cells 2009, 9, 432–438. [CrossRef]
66. Naik, N.S.; Padaki, M.; Déon, S.; Murthy, D.H. Novel poly(ionic liquid)-based anion exchange membranes for efficient and rapid
acid recovery from industrial waste. Chem. Eng. J. 2020, 401, 126148. [CrossRef]
67. Mondal, R.; Pal, S.; Chatterjee, U. Alkylated imidazole moieties in a cross-linked anion exchange membrane facilitate acid
recovery with high purity. ACS Appl. Polym. Mater. 2021, 3, 1544–1554. [CrossRef]
68. Palatý, Z.; Bendová, H. Separation of HCl+FeCl2 mixture by anion-exchange membrane. Sep. Purif. Technol. 2009, 66, 45–50.
[CrossRef]
69. Cheng, C.; Yang, Z.; Pan, J.; Tong, B.; Xu, T. Facile and cost effective pva based hybrid membrane fabrication for acid recovery.
Sep. Purif. Technol. 2014, 136, 250–257. [CrossRef]