membranes

Article
Novel Polymeric Thin-Film Composite Membranes
for High-Temperature Gas Separations
Fynn Weigelt 1,2,† , Sara Escorihuela 1,2,† , Alberto Descalzo 1,2 , Alberto Tena 1, * ,
Sonia Escolástico 2 , Sergey Shishatskiy 1 , Jose Manuel Serra 2, * and Torsten Brinkmann 1, *
1 Helmholtz-Zentrum Geesthacht, Institute of Polymer Research, Max-Planck-Str.1, 21502 Geesthacht,
Germany; fynn.weigelt@hzg.de (F.W.); saesro@itq.upv.es (S.E.); albertodescalzo5@gmail.com (A.D.);
sergey.shishatskiy@hzg.de (S.S.)
2 Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones,
Científicas, Avda. Los Naranjos, s/n, 46022 Valencia, Spain; soesro@upvnet.upv.es
* Correspondence: alberto.tena@hzg.de (A.T.); jmserra@itq.upv.es (J.M.S.); torsten.brinkmann@hzg.de (T.B.)
† These authors contributed equally to this work.




Received: 13 March 2019; Accepted: 8 April 2019; Published: 10 April 2019


Abstract: Novel selective polymeric thin-film composite membranes (TFCMs) for applications at
elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218® and
6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase
inversion process. The TFCM properties were investigated with different gases in a wide temperature
range, including temperatures up to 270 ◦ C. The membranes showed very high thermal stability
and performed well at the elevated temperatures. The development of highly thermally resistant
polymeric membranes such as these TFCMs opens opportunities for application in high-temperature
integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to
maximize H2 yield.

Keywords: thin-film composite membranes; high-temperature applications; high thermal stability;

hydrogen; carbon dioxide

1. Introduction
Membranes offer attractive opportunities for a great number of gas separation applications,
such as air separation, hydrogen purification, or natural gas upgrading [1]. Considering the nature
of the membrane selective layer, membranes can be classified as polymeric, metallic, ceramic, and
carbonaceous [1–3]. Materials are selected according to the application conditions and requirements.
Although polymeric membranes exhibit clear benefits in terms of processability and relatively low
price, they also have some drawbacks, such as low thermal and chemical stability, that have to be
carefully considered with respect to the selected application [4].
In order to apply the selective materials in an industrial process, the polymeric membranes
must be processed as a thin selective layer (<100 nm). Since the layer is very thin, the materials
must be supported [5–7]. One method to obtain a supported selective layer is by the formation of
thin-film composite membranes (TFCMs). In this case, the supporting structures should possess good
mechanical properties and, together with the selective layer, should have high thermal and chemical
stability, whilst simultaneously being highly permeable. Obviously, a thinner selective layer leads to
higher flux through the membrane. The multilayer concept of TFCMs is very attractive in terms of
simplicity and cost compared to integral asymmetric membranes, where the material of the selective
layer needs to be the same as the material of the porous support. This fact opens the way for practical
use of expensive tailor-made polymers and other materials which are often too expensive or not

Membranes 2019, 9, 51; doi:10.3390/membranes9040051 www.mdpi.com/journal/membranes

Membranes 2019, 9, 51 2 of 13

stable enough to be used for the formation of the whole membrane structure [8]. There are multiple
materials with promising properties for specific applications but with applicability limitations such as
in cost, upscaling, stability, or mechanical or other physical-chemical properties. These problems can
be solved by using inexpensive materials as porous support, and by placing a very thin layer of the
selective—and more expensive—material on top [6,7]. In this way, we can match the selective layer
and the support material for a specific application.
Typical polymeric supporting materials are made from commercial materials such as
polyacrylonitrile or polyetherimide [6,9,10]. These porous support materials are not stable at elevated
temperatures (greater than 180–200 ◦ C). This issue can be solved by using more thermally stable
supports, such as ceramics. The main limitation of this approach is the compatibility between ceramic
support and the polymeric layer. This problem was solved by studying the limitations of the coating
process [11]. Despite the high thermal and chemical stability, the use of ceramic supports presents
some limitations [12], especially in terms of compatibility with the polymeric layer. In terms of the
selective layer, glassy polyimides present excellent separation properties as well as very good thermal
and chemical stability [13–16]. Therefore, the ideal situation can be found when both support and
selective layer are polymeric materials.
In polymeric gas separation membranes, the mass transfer is described according to the
solution–diffusion mechanism [1]. In the solution–diffusion theory of molecular transport in polymers,
the permeability (Pi ) coefficient is determined by two factors (Equation (1)): The solubility, Si , related
to the properties of the gas and to its interaction with the polymer matrix. It reflects the number of
molecules dissolved in the membrane material. Since it depends on molecular interaction, it is an
equilibrium term. On the other hand, the diffusivity, Di , depends mainly on the ability of the gas
molecules to move through the bulk of a polymer by migrating from one free volume void to another.

Pi = Di ·Si (1)

At elevated temperatures, as in the case of several industrial processes, the solubility factor becomes
less important compared to the more dominant diffusivity factor compared to ambient temperatures.
Therefore, under the here-described conditions, the major influence of the permeability selectivity
(Equation (2)) is mostly seen in the differences in the diffusion coefficients of gases dissolved in the
polymer. An additional explanation employs the temperature dependencies of the two coefficients.
The heat of sorption ∆HS consists of the heat of mixing and the heat of condensation, and can be
either positive or negative [17]. The activation energy of diffusion Ed is always positive, and for
permanent gases its absolute value always is considerably larger than the absolute value of the heat of
sorption [18]. " #" #
Di Si
αij = αD ·αS = · (2)
Dj Sj
Especially for polymers, this consideration limits the choice of selective materials to glassy
polymers, where permeability selectivity is directed by the diffusion selectivity, and not by the
solubility selectivity. The largest use of syngas is hydrogen production, where steam methane
reforming (SMR) is the predominant technology. The latter is a well-established process with two main
reactions: reforming and water-gas shift (WGS) reactions [12,19,20].
The endothermic methane steam reforming reaction is:

kJ
CH4 + H2 O
CO + 3H2 ∆H = +206.2 . (3)
mol
Afterwards, the carbon monoxide reacts further with steam to form H2 and CO2 , by the weakly
exothermic water-gas shift reaction:

kJ
CO + H2 O
CO2 + H2 ∆H = −41.2 (4)
mol
Membranes 2019, 9, 51 3 of 13

In order to use this hydrogen, a purification step of the mixture CO, CO2 , and H2 is necessary. The
composition of the mixture varies depending on the source and the intended use of the synthesis gas.
A typical example is ammonia synthesis, where the gas exiting the low-temperature water-gas shift
reaction contains 44% hydrogen, 13% CO2 , and 28% water, among other gases [21]. Low-temperature
WGS reactors using Cu-Zn catalyst systems are operated at about 200 ◦ C [21]. For high-temperature
WGS reactors employing Fe-CR catalysts, membranes that can withstand temperatures above 300 ◦ C
and upstream pressures of up to 2.7 MPa are needed [22].
In the literature there are only a few works available discussing high-temperature measurements
of polymeric gas separation membranes. Most of them are about hollow fiber polybenzimidazole
(PBI) membranes [23–25]. Costello and Koros describe dense films of 6FDA-6FpDA and 6FDA-6FmDA
membranes at elevated temperatures up to 300 ◦ C [26].
To expand the applicability of polymeric materials to these types of high-temperature processes, it
is necessary to provide new thermally and chemically stable porous support structures to produce
TFCMs. Therefore, in this work, a highly thermally resistant polymeric porous support is developed
and combined with dense layers of thermally stable polymers. The characterization was performed
taking into account the later application for hydrogen separation. Efforts were carried out to improve
the membrane stability, enabling its operation temperature up to 270 ◦ C. This is a temperature range
which is interesting for separation processes in the petrochemical industry and for use in catalytic
membrane reactors.

2. Experimental

2.1. Materials

2.1.1. Non-Woven Support

The non-woven polyphenylene sulfide (PPS) has a high porosity as well as excellent thermal and
chemical stabilities. The supplier cannot be disclosed due to license issues.

2.1.2. Polymers
Polybenzimidazole (PBI), a poly[2,20 -(m-phenylene)-5,50 -bibenimidazole], was purchased from
PBI® Performance products, Inc. (Charlotte, NC, USA) in a 26 wt. % solution. Polyethylene glycol
(PEG) with an average molecular weight of 2000 g mol−1 was obtained from Sigma-Aldrich (St. Louis,
MO, USA). The polyimide Matrimid® 5218 (Matrimid® ) was purchased from Huntsman Advanced
Materials GmbH (Berkamen, Germany) in powder form. The polyimide 6FDA-6FpDA was synthesized
for the current work according to procedure described elsewhere [27]. Teflon® AF 2400 was purchased
from E. I. du Pont de Nemours (Wilmington, DE, USA).

2.1.3. Solvents
Tetrahydrofuran (THF), dimethyl acetamide (DMAc), and toluene were purchased from Merck
GmbH (Darmstadt, Germany). 3MTM FluorinertTM FC-770, >99%, was purchased from IOLITEC Ionic
Liquids Technologies GmbH (Heilbronn, Germany). All solvents were used as received.

2.1.4. Gases
Gases were purchased from Linde AG and had purities of at least 99.99%.

2.2. Membranes

2.2.1. Thick Films

Dense homogeneous films of Matrimid® , 6FDA-6FpDA, and Teflon® AF 2400 were prepared by
casting the polymer solution (in THF and FC-770 for Teflon® AF 2400) on a leveled glass plate and
Membranes 2018, 8, x FOR PEER REVIEW 4 of 12

membranes were dried for 6 h at 200 °C under vacuum. The thickness of the homogenous membranes
was determined using a Fischer Deltascope FMP10 (Helmut Fischer GmbH, Sindelfingen, Germany).
The thickness
Membranes 2019, 9,of
51 the Matrimid dense film was 30.1 ± 0.1 μm, the thickness of the 6FDA-6FpDA
® was
4 of 13
16.8 ± 0.1 μm, and the thickness of the Teflon® AF 2400 was 25.4 ± 0.1 μm.

drying under constant

2.2.2. Preparation dry nitrogen flow. When the solvent evaporation was complete, the membranes
of TFCMs
were dried for 6 h at 200 ◦ C under vacuum. The thickness of the homogenous membranes was
The porous
determined usingsupport
a FischerforDeltascope
the TFCMs (Figure
FMP10 1) wereFischer
(Helmut prepared on a Sindelfingen,
GmbH, non-woven PPS support on
Germany). Thea
lab-scale membrane casting
® machine [28]. First the purchased PBI solution was diluted
thickness of the Matrimid dense film was 30.1 ± 0.1 µm, the thickness of the 6FDA-6FpDA was with DMAc
to the
16.8 concentration
± 0.1 µm, and theofthickness
18 wt. %ofofthe
PBI. As a®porosity
Teflon AF 2400modifier,
was 25.4 6± wt. % PEG 2000 was added to the
0.1 µm.
solution. On the lab-scale casting machine, the PBI solution was cast on the non-woven PPS and the
porous
2.2.2. PBI support
Preparation was obtained by phase inversion [29]. Water was used as a non-solvent of the
of TFCMs
coagulation bath at a temperature of 20 °C. After the casting, the porous support was extensively
The porous support for the TFCMs (Figure 1) were prepared on a non-woven PPS support on a
washed with an excess of hot water and dried afterwards.
lab-scale membrane casting machine [28]. First the purchased PBI solution was diluted with DMAc
TFCMs were coated by a dip-coating process. The porous support was first dipped in toluene in
to the concentration of 18 wt. % of PBI. As a porosity modifier, 6 wt. % PEG 2000 was added to the
order to fill the pores. Subsequently, the samples were dip coated with the polymer solution (4 wt. %
solution. On the lab-scale casting machine, the PBI solution was cast on the non-woven PPS and the
Matrimid® or 3.5 wt. % 6FDA-6FpDA) and subsequently dried at 50 °C for 24 h. Afterwards, the
porous PBI support was obtained by phase inversion [29]. Water was used as a non-solvent of the
samples were dip coated in a solution of 1 wt. % Teflon® AF2400 in FC 770 to get a protective layer.
coagulation bath at a temperature of 20 ◦ C. After the casting, the porous support was extensively
Time of dip coating was controlled to 10 s. The TFCMs were dried in an oven under vacuum for 24 h
washed with an excess of hot water and dried afterwards.
at 260 °C to ensure that all the solvent used during the process was evaporated [30].

Figure 1.
Figure 1. Sketch
Sketch of
of the
the production
production steps
steps toto form
form thin-film
thin-filmcomposite
composite membranes
membranes (TFCMs)
(TFCMs) with
with four
four
layers:
layers: polyphenylene
polyphenylene sulfide (PPS) as as aa non-woven
non-woven support,
support, polybenzimidazole
polybenzimidazole (PBI)
(PBI) as
as aa porous
porous
support, Matrimid®® or 6FDA-6FpDA as a selective layer, and Teflon
support, Matrimid Teflon® AF 2400
® AF 2400 as a protective layer.

TFCMs were coated

2.3. Characterization by a dip-coating process. The porous support was first dipped in toluene in
Methods
order to fill the pores. Subsequently, the samples were dip coated with the polymer solution (4 wt. %
The “time-lag” and the “pressure increase” (variable pressure, constant volume [31]) methods
Matrimid® or 3.5 wt. % 6FDA-6FpDA) and subsequently dried at 50 ◦ C for 24 h. Afterwards, the
for thick dense films and for TFCMs, respectively, were used to determine the gas transport
samples were dip coated in a solution of 1 wt. % Teflon® AF2400 in FC 770 to get a protective layer.
parameters. The temperature ranged from 30 to 70 °C and a 100 mbar feed pressure was used for H2,
Time of dip coating was controlled to 10 s. The TFCMs were dried in an oven under vacuum for 24 h at
N2, O2, CO2, and CH4. The first method relied on maintaining a constant feed pressure while
260 ◦ C to ensure that all the solvent used during the process was evaporated [30].
monitoring the permeate pressure, which changed as a function of time due to the transport of gas
molecules
2.3. through Methods
Characterization the membrane. The measurement of the increase in pressure in the permeate
chamber of known constant volume started at the time point when the gas at the constant pressure
The “time-lag” and the “pressure increase” (variable pressure, constant volume [31]) methods for
was brought in contact with the membrane. The time-lag, θ, was determined by extrapolating the
thick dense films and for TFCMs, respectively, were used to determine the gas transport parameters.
slope of the linear increase to its intersection with the time axis. Additionally, the gas permeability
The temperature ranged from 30 to 70 ◦ C and a 100 mbar feed pressure was used for H2 , N2 , O2 ,
coefficient of the membrane was calculated from the linear part of the curve. The permeability (Peff,i)
CO2 , and CH4 . The first method relied on maintaining a constant feed pressure while monitoring
of a gas penetrant i is the pressure or fugacity difference (i.e., driving force) and thickness-normalized
the permeate pressure, which changed as a function of time due to the transport of gas molecules
flux of the component through the membrane and is defined by:
through the membrane. The measurement of the increase in pressure in the permeate chamber of
known constant volume started at the time point when the gas at the constant pressure was brought
in contact with the membrane. The time-lag, θ, was determined by extrapolating the slope of the
linear increase to its intersection with the time axis. Additionally, the gas permeability coefficient
of the membrane was calculated from the linear part of the curve. The permeability (Peff,i ) of a gas
Membranes 2019, 9, 51 5 of 13

penetrant i is the pressure or fugacity difference (i.e., driving force) and thickness-normalized flux of
the component through the membrane and is defined by:

Ni l
Pe f f ,i = , (5)
Am ∆pi

where Peff,i is the permeability of component i, Ni is the volumetric flowrate of the component i at
standard conditions (STP) through the membrane, Am is the membrane area, and ∆pi the partial
pressure (or fugacity) difference between feed and permeate sides. The single gas permeance Leff,i can
be calculated by:
Pe f f ,i Ni
Le f f ,i = = . (6)
l Am ∆pi
The volumetric flowrate was determined from the permeate pressure change with time assuming
that the ideal gas law is applicable in the pressure range of 0–10 mbar (i.e., the working range of
the permeate-side pressure sensor). The ideal selectivity α of a dense gas separation membrane is
defined as:
P L
αi,j = i = i , (7)
Pj Lj
where Pi and Pj are the permeabilities of gases i and j.
A custom-built machine was used for the “time-lag” and “pressure-increase” measurements. The
machine employs two software based evaluation modes: one designed for experiments involving thick
isotropic films and allowing for determination of the diffusion, solubility, and permeability coefficients
of gases; and the second designed for the determination of the gas transport properties of practical
membranes having selective layers thin enough to neglect the time lag caused by the diffusion of gas
molecules through the bulk of the selective layer material.
Single gas measurements at high temperature were performed in a module designed for this
purpose. The set-up (Figure 2) consisted of: (a) three mass flow controllers (MF_1–MF_3) for H2 and
CO2 as feed gases and Ar as sweep gas; (b) two manometers to control the internal pressure in both
chambers of the reactor (feed side and permeate side); (c) a micro GC to measure the outlet gases at the
permeate side; and finally (d) a reactor with two chambers that allow the membrane to be placed and
sample to be sealed by rubber rings in the center. Membranes were placed in the center of the reactor
and sealed from both sides. Hence, two well-defined chambers separated by the membrane sample
allowed us to perform measurements at different temperatures.
Fluxes (Ji ), in mLSTP m−2 s−1 , of H2 and CO2 permeating through the membrane were calculated
by dividing the gas concentration by the effective surface area of the membranes Am , as shown in the
following equation:
%i ·Qsweep
Ji = . (8)
Am
Afterwards, flux was divided by the gas partial pressure difference (∆pi ) between the two chambers,
and the permeance of the specific gas could be obtained. In order to compare the permeances, the
units were converted to mSTP 3 m−2 h−1 bar−1 .

Ji
Pi = (9)
∆pi
Differential scanning calorimetry (DSC) experiments were carried out using the calorimeter DSC 1
(Mettler-Toledo, Gießen, Germany) with the following parameters: nitrogen atmosphere, heating rate
10 K/min, temperature range from room temperature to 380 ◦ C. Three heating-cooling cycles were
conducted with a five-minute isotherm interval between the heating and the cooling, whereas the first
heating interval served to erase the sample history from the sample preparation (start temperature: RT,
maximal temperature: 180 ◦ C), while the other two cycles were applied for the determination of thermal
properties. The latter cycles were accomplished in the temperature range 200–380 ◦ C. In this setting,
The machine employs two software based evaluation modes: one designed for experiments involving
thick isotropic films and allowing for determination of the diffusion, solubility, and permeability
coefficients of gases; and the second designed for the determination of the gas transport properties
of practical membranes having selective layers thin enough to neglect the time lag caused by the
diffusion of gas
Membranes 2019, molecules through the bulk of the selective layer material.
9, 51 6 of 13
Single gas measurements at high temperature were performed in a module designed for this
purpose. The set-up (Figure 2) consisted of: (a) three mass flow controllers (MF_1–MF_3) for H2 and
the second heating interval was used for the evaluation of the glass transition and the third heating
CO2 as feed gases and Ar as sweep gas; (b) two manometers to control the internal pressure in both
interval was used as verification. The glass transition temperature Tg was considered as the inflection
chambers of the reactor (feed side and permeate side); (c) a micro GC to measure the outlet gases at
point of the heat flow as a function of the temperature with the onset method using the instrumentation
the permeate side; and finally (d) a reactor with two chambers that allow the membrane to be placed
software. The midpoints were also estimated using this software. For the measurement, approximately
and sample to be sealed by rubber rings in the center. Membranes were placed in the center of the
10 mg of the vacuum dried polymer and the ground composites were placed in an aluminum pan of
reactor and sealed from both sides. Hence, two well-defined chambers separated by the membrane
10 µL.
sample allowed us to perform measurements at different temperatures.

Figure 2. High-temperature set-up for polymeric membranes.

Figure 2. High-temperature set-up for polymeric membranes.
Thermogravimetric analysis (TGA) was carried out using a TG 209 F1 Iris (Netzsch, Selb,
Germany). The experimental setup was as follows: temperature range 30–800 ◦ C, heating rate 10 K/min,
nitrogen atmosphere.
The morphology of the membranes was determined by scanning electron microscope (Merlin
and Auriga; Carl Zeiss GmbH, Oberkochen, Germany). For this analysis the samples were either
cryo-fractured in liquid nitrogen or cut with a focused gallium ion beam (FIB). Afterwards, the samples
were sputter-coated with carbon.

3. Results and Discussion

The glass transition temperature (Tg ) was determined by DSC. The Tg of Matrimid® is 320 ◦ C and
the Tg of 6FDA-6FpDA is 310 ◦ C, as reported in previous works [11,32]. The Tg of the PBI was 427 ◦ C.
These values clearly indicate the applicability of the chosen materials for application in the desired
temperature range above 200 ◦ C.
From the TGA curves in Figure 3, it is observed that the different polymeric materials showed
high thermal stability. The decomposition started above 300 ◦ C for each polymer.
The cross-sectional morphology of the porous PBI and the prepared TFCMs was analyzed. The
cross section of the porous support is presented in Figures 4 and 5. In the lower part of Figure 4
the non-woven PPS fibers and the porous PBI layer on top can be seen. The porous PBI layer had a
thickness of approximately l ≈ 30 µm, average pore size of about 100 nm, and a surface porosity of
approximately 21%. The nitrogen permeance of the porous PBI was 459 mSTP 3 m−2 h−1 bar−1 , and the
permeances of the other gases were in agreement with Knudsen-type gas flow through porous media.
 The glass transition temperature (Tg) was determined by DSC. The Tg of Matrimid® is 320 °C and
the Tg of 6FDA-6FpDA is 310 °C, as reported in previous works [11,32]. The Tg of the PBI was 427 °C.
These values clearly indicate the applicability of the chosen materials for application in the desired
temperature range above 200 °C.
From
Membranes 2019,the TGA curves in Figure 3, it is observed that the different polymeric materials showed
9, 51 7 of 13
high thermal stability. The decomposition started above 300 °C for each polymer.
Membranes 2018, 8, x FOR PEER REVIEW 7 of 12

The cross-sectional morphology of the porous PBI and the prepared TFCMs was analyzed. The
cross section of the porous support is presented in Figures 4 and 5. In the lower part of Figure 4 the
non-woven PPS fibers and the porous PBI layer on top can be seen. The porous PBI layer had a
thickness
Membranesof approximately
2018, l ≈ 30 μm, average pore size of about 100 nm, and a surface porosity
8, x FOR PEER REVIEW 7 of 12 of
approximately 21%. The nitrogen permeance of the porous PBI was 459 mSTP ·m ·h ·bar , and the
3 −2 −1 −1
The cross-sectional morphology of the porous PBI and the prepared TFCMs was analyzed. The
permeances of the other gases were in agreement with Knudsen-type gas flow through porous media.
cross section of the porous support is presented in Figures 4 and 5. In the lower part of Figure 4 the
non-woven PPS fibers and the porous PBI layer on top can be seen. The porous PBI layer had a
thickness of approximately l ≈ 30 μm, average pore size of about 100 nm, and a surface porosity of
approximately 21%. The nitrogen permeance of the porous PBI was 459 mSTP3·m−2·h−1·bar−1, and the
permeances ofFigureFigure
the 3.3.TGA
other TGAthermographs
gases thermographs forthe
for
were in agreementthe different
different
with polymericmaterials
polymeric
Knudsen-type materials
gas flow inin dry
dry Ar.
through Ar.
porous media.

Figure 4. (a) SEM cross section of the support of non-woven PPS and porous PBI structure; (b) SEM
surface of the porous PBI structure; and (c) SEM cross section of the porous PBI structure.

Figure 5a shows a higher magnification for the cross section of the porous PBI. In this case, the
Figure 4. (a) SEM cross section of the support of non-woven PPS and porous PBI structure; (b) SEM
sampleFigure
was cut bySEM
4. (a) FIB.cross
The section
anisotropic nature of
of the support the porousPPS
of non-woven PBIand
structure canstructure;
porous PBI be clearly
(b)seen,
SEM as can
surface of the porous PBI structure; and (c) SEM cross section of the porous PBI structure.
pores on the membrane
surface of the poroussurface.
PBI structure; and (c) SEM cross section of the porous PBI structure.

Figure 5a shows a higher magnification for the cross section of the porous PBI. In this case, the
sample was cut by FIB. The anisotropic nature of the porous PBI structure can be clearly seen, as can
pores on the membrane surface.

(a) SEM
Figure 5. (a) SEM cross
cross section
section of porous PBI structure; (b) SEM cross-section of the TFCM with a
® and Teflon®® AF 2400 protective layer; and (c) SEM cross section
selective layer of Matrimid® and Teflon AF 2400 protective layer; and (c) SEM cross section of the
TFCM ® AF 2400 protective layer.
TFCM with a selective layer of 6FDA-6FpDA and
with a selective layer of 6FDA-6FpDA and Teflon
Teflon® AF 2400 protective layer.
Figure 5. (a) SEM cross section of porous PBI structure; (b) SEM cross-section of the TFCM with a
Figure 5b
Figure 5a shows the a higher magnification for the cross section of the porous PBI.®In this case, the
selective shows cross-sectional
layer of Matrimid ® and Teflonmorphology for the
® AF 2400 protective TFCM
layer; andwith a Matrimid
(c) SEM cross sectionselective
of the layer.
sample was
The Matrimid cut
TFCM with by
® layerFIB. The
showed
a selective anisotropic
layera of
thicknessnature
6FDA-6FpDA of
of about the porous
1 μm® AF
and Teflon whilePBI
2400the structure
thickness
protective can be clearly seen,
layer.of the Teflon® AF 2400 as can
pores on the membrane surface.
protective layer was estimated to be under 80 nm. The selective layer and the protective layers were
Figure 5b5bshows ® selective layer.
Figure
homogenous, showsthe
without thecross-sectional
visible defects. Nomorphology
cross-sectional morphology
penetrationfor for the TFCM
the
of the TFCMwith
Matrimid withaaMatrimid
® into Matrimid
the pores
® selective layer.
was observed.
The Matrimid ® ®
The 4c showslayer
Matrimid layer showed
showed aa thickness
thickness aboutof
of about 11 μm
µm while
the while
TFCMthe the thickness
thickness ofofthe
theTeflon
Teflon AF
as theAFselective
24002400
® ®
Figure the cross-sectional morphology with 6FDA-6FpDA
protective
protective layer
layer waswas estimated
estimated to
to be
be under
under 80
80 nm.
nm. The
The selective
selective layer
layer and
and
layer. According to Figure 5c, the selective layer of 6FDA-6FpDA had a thickness of about 1 μm and the
theprotective
protective layers
layerswerewere
homogenous, without visible defects. No2400
penetration of ®®
homogenous,
the protective without
layer on visible
top defects.
of Teflon ® AFNo penetration of the
was estimated theMatrimid
Matrimid into
into
to have a thickness the pores
the pores
of was
100 was
nm.observed.
observed.
Figure 5c
Figure
Figure 4c 4c shows
shows thethe cross-sectional
cross-sectional morphology
morphology of of
the the
TFCMTFCM with with 6FDA-6FpDA
6FDA-6FpDA as as
the the selective
selective layer.
shows evidence of 6FDA-6FpDA penetration into the pores of the PBI substrate, which was filled
layer. According
According to Figure to 5c,
Figure
the 5c, the selective
selective layer layer
of of 6FDA-6FpDA
6FDA-6FpDA had had
a a thickness
thickness of of about
about 1 1 μmand
µm andthe
with toluene to prevent polymer penetration during the membrane preparation. In this case, the
the protective layer
protective onoftopTeflon ® AF
of Teflon ® AF 2400 was estimated to have a thickness of 100 nm. Figure 5c
polyimide layer
couldon top
withstand the presence 2400 was estimated
of toluene to have a thickness
in the polymer/THF solution ofwithout
100 nm.going Figure 5c
into
shows evidence
shows inversion.
evidence of of 6FDA-6FpDA
6FDA-6FpDA penetration
penetration into the
into the pores of the PBI substrate, which was filled
phase Therefore, the presence of toluene in pores
the PBI ofstructure
the PBI substrate,
resulted not which
just was filled
in partial
with
with toluene
toluene to toprevent
preventpolymer
polymerpenetration
penetration during
during the the membrane
membrane preparation.
preparation. InInthis
thiscase,
case,thethe
polyimide
polyimide penetration
could withstandinto the thepores but also
presence in toluene
of toluene in the penetration
polymer/THF intosolution
the coating solution
without goingasinto well,
causing partial phase inversion in the coating polymer solution during the
phase inversion. Therefore, the presence of toluene in the PBI structure resulted not just in partial selective layer drying.
This could explain
polyimide the difference
penetration in gas
into the pores buttransport results
also in toluene for the TFCM
penetration and
into the isotropic
coating 6FDA-6FpDA
solution as well,
film
causing partial phase inversion in the coating polymer solution during the selective layerfrom
discussed below, as well as the differences in the selective layer thickness estimated drying. SEM
This could explain the difference in gas transport results for the TFCM and isotropic 6FDA-6FpDA
film discussed below, as well as the differences in the selective layer thickness estimated from SEM
Membranes 2019, 9, 51 8 of 13

polyimide could withstand the presence of toluene in the polymer/THF solution without going into
phase inversion. Therefore, the presence of toluene in the PBI structure resulted not just in partial
polyimide penetration into the pores but also in toluene penetration into the coating solution as well,
causing partial phase inversion in the coating polymer solution during the selective layer drying. This
could explain the difference in gas transport results for the TFCM and isotropic 6FDA-6FpDA film
discussed below, as well as the differences in the selective layer thickness estimated from SEM images
and from gas transport measurements. This was not the case for the Matrimid® , where toluene did
not allow the polymer to penetrate into the PBI porous structure and, therefore, the selective layer
thickness estimated from SEM and gas transport analysis were in good agreement.
The time-lag method was used for the evaluation of the permeability coefficients of the Matrimid®
and 6FDA-6FpDA thick films for H2 , CO2 , O2 , CH4 , and N2 in the temperature range 30–70 ◦ C,
at 1000 mbar feed pressure (Table 1). The ideal gas perm-selectivities at 30 ◦ C were αH2/CO2 = 2.6,
αO2/N2 = 6.2, and αCO2/CH4 = 35.7 for Matrimid® and αH2/CO2 = 1.4, αO2/N2 = 5.4, and αCO2/CH4 = 47.6
for 6FDA-6FpDA. The activation energy (EA,i ) of permeability was calculated from data obtained in
the range 30–70 ◦ C and is defined from the Arrhenius equation as:
−EA,i
Pi (T ) = P0,i ·e R·T , (10)

where Pi is the permeability, P0,i is the pre-exponential factor, R is the universal gas constant, and T is
the temperature.

Table 1. Separation properties for the thick films at 30 ◦ C and the activation energy calculated in the
temperature range 30–70 ◦ C.

Gases Selectivity (-)

Polymer Parameter
H2 CO2 O2 CH4 N2 O2 /N2 CO2 /CH4
Permeability (Barrer) * 18.9 7.14 1.62 0.20 0.26 6.2 35.7
Matrimid®
EA (kJ mol−1 ) 13.0 8.15 8.93 18.0 22.6 - -
Permeability (Barrer) * 74.3 53.4 10.3 1.12 1.89 5.4 47.6
6FDA-6FpDA
EA (kJ mol−1 ) 3.67 0.57 3.31 7.02 6.43 - -
Teflon® AF Permeability (Barrer) * 1180 1248 504 155 222 2.3 8.1
2400 EA (kJ mol−1 ) 5.14 −3.01 3.40 9.12 7.38 - -
* 1 Barrer = 10−10 cmSTP 3 cm−1 s−1 cmHg−1 .

The pressure increase method was used for the H2, CO2 , O2 , CH4 , and N2 permeance evaluation
of the TFCMs with selective layers of Matrimid® and 6FDA-6FpDA and the Teflon AF 2400 protective
layer. As in the case of the thick films, the pure gas permeance data was acquired for the TFCMs in the
temperature range 30–70 ◦ C and the data for 30 ◦ C are presented in Table 2. The selectivities in the case
of the Matrimid® membrane were αH2/CO2 = 2.2, αO2/N2 = 6.4, and αCO2/CH4 = 35.2; for 6FDA-6FpDA
they were αH2/CO2 = 1.1, αO2/N2 = 4.1, and αCO2/CH4 = 33.6 at 30 ◦ C. The Matrimid® TFCMs selectivities
agree with the selectivities of the thick film membranes, whilst for the 6FDA-6FpDA TFCMs the
selectivities were lower than the ideal selectivities calculated from permeability coefficients. The
same trend was observed in the activation energies of the 6FDA-6FpDA membranes. The EA values
of the Matrimid® TFCMs were in good agreement with the EA values of the thick-film membranes.
For 6FDA-6FpDA, a decrease of the activation energies in the TFCMs was observed. A possible
explanation could be the influence of the Teflon® AF 2400 protective layer on overall membrane
performance. Table 1 displays the permeabilities and EA values of the Teflon AF 2400. Teflon AF 2400
had high permeabilities and low selectivities. The selectivities for Teflon® AF 2400 were αH2/CO2 = 1.0,
αO2/N2 = 2.3, and αCO2/CH4 = 8.1 at 30 ◦ C. In Table 2, the estimated selective layer thicknesses are
presented, as calculated from the gas transport data obtained for isotropic polymer films and TFCMs
(i.e., by dividing the permeability by the permeance). For Matrimid® TFCM the calculated selective
Membranes 2019, 9, 51 9 of 13

layer thickness was in agreement with the estimated thickness from the SEM image (Figure 5). For
6FDA-6FpDA the calculated selective layer thickness was lower than the estimated layer thickness
from the SEM image (Figure 5c). This could explain the difference in the EA values for the TFCM of
6FDA-6FpDA, which may have originated from the observed penetration and partial phase inversion
of the 6FDA-6FpDA in Figure 5c. Therefore, the protective Teflon® AF 2400 layer appeared to have a
significant influence on the permeance of the 6FDA-6FpDA TFCM. The Teflon® AF 2400 was selected
based on its high permissibility to the transport of the gases and due to its high thermal stability.
From this, it can be inferred that a much thinner layer of the protective fluorinated polymer should be
applied for a fast polymer such as 6FDA-6FpDA.

Table 2. Separation properties for the thin-film composite membranes at 30 ◦ C and the activation
energy calculated in the temperature range from 30 to 70 ◦ C.

Gases
Polymer Parameter
H2 CO2 O2 CH4 N2
Permeance, 102 3
(mSTP m 2 h−1 bar−1 )
* 4.57 2.11 0.51 0.06 0.08
Matrimid® Activation Energy (EA ) (kJ mol−1 ) 12.3 6.24 7.13 20.0 14.6
Selective layer thickness ** (nm) 1120 930 870 1280 1330
Permeance, 102 (mSTP 3 m−2 h−1 bar−1 ) * 46.1 41.3 8.35 1.23 2.05
6FDA-6FpDA Activation Energy (EA ) (kJ mol−1 ) 5.58 −3.45 3.08 8.95 6.51
Selective layer thickness ** (nm) 440 350 340 250 250
* 1 mSTP 3 m−2 h−1 bar−1 = 1.239 × 10−10 mol m−2 s−1 Pa−1 ; 1000 GPU = 2.700 mSTP 3 m−2 h−1 bar−1 . ** The thickness
of the selective layer estimated from gas transport data obtained for isotropic polymer film and TFCM.

The high-temperature gas transport measurement method was used for the evaluation of the
permeance of the TFCMs with the selective layers of Matrimid® and 6FDA-6FpDA for the gases H2
and CO2 . The pure gas permeance data were obtained for the two TFCMs in the temperature range
30–270 ◦ C at 1 bar feed pressure and sweep gas flowrate 50 mL min−1 . The permeance and selectivity
values are presented in Table 3. It was possible to conduct reproducible gas transport measurements
for the TFCMs up to 275 ◦ C, which is in accordance with the TGA measurements (Figure 3). The
temperature limit was imposed by the PPS non-woven support, as it started to melt at this point,
causing the membrane to break. The H2 /CO2 selectivity for Matrimid® was αH2/CO2 = 1.9 and for
6FDA-6FpDA it was αH2/CO2 = 1.1 at 30 ◦ C, which are in good agreement with the data of pressure
increase measurements. Since the activation energy for CO2 (EA,CO2 ) is lower than EA,H2 , the H2 /CO2
selectivities increased with the temperature for both membranes. For the 6FDA-6FpDA, a change in
the EA values for CO2 was observed. The evolution of the permeance with the temperature for the
gases H2 and CO2 is shown in Figure 6. In the case of Matrimid® (Figure 6a), a simple Arrhenius
behavior was observed for both gases. Figure 6b shows the evolution of the permeance with reciprocal
temperature for the 6FDA-6FpDA. H2 permeance followed a simple Arrhenius behavior in the range
from 30 to 270 ◦ C, while CO2 permeance exhibited a change in apparent EA values for temperatures
above 170 ◦ C for CO2 . The absolute change of the gas permeance of CO2 in the 6FDA-6FpDA TFCM
was very small, from 0.22 mSTP 3 m−2 h−1 bar−1 at 30 ◦ C to 0.19 mSTP 3 m−2 h−1 bar−1 at 266 ◦ C, while
the corresponding EA in a thick film of 6FDA-6FpDA (Table 1) was nearly 0 kJ mol−1 . Therefore, further
experiments will be done to analyze this observation.
Membranes 2019, 9, 51 10 of 13

Table 3. Single gas separation properties and activation energies (EA ) for the thin-film composite
membranes in the range of temperatures between 30 and 266 ◦ C for the gas pair CO2 and H2 . The EA
values were calculated between 30 and 266 ◦ C.

Matrimid® 6FDA-6FpDA
Permeance, 102 (mSTP 3 m−2 h−1 bar−1 )
T (◦ C) H2 CO2 αH2/CO2 H2 CO2 αH2/CO2
30 3.86 2.05 1.88 24.2 22.0 1.10
78 7.40 2.30 3.22 40.1 20.0 2.01
125 12.0 2.62 4.58 56.5 16.6 3.40
173 18.0 2.92 6.16 76.0 16.8 4.52
202 21.4 3.09 6.92 89.6 17.3 5.18
230 25.0 3.21 7.89 101 18.0 5.61
248 27.5 3.24 8.49 107 18.4 5.82
266 29.3 3.31 8.85 118 18.8 6.28
Membranes 2018, 8, x−1FOR PEER REVIEW −2.91 (30–125 ◦ C) 10 of 12
EA 2018,
(kJ mol ) PEER11.8
REVIEW 2.89 - 9.02 -
Membranes 8, x FOR 2.45 (173–266 ◦ C) 10 of 12

Figure 6. (a) Arrhenius plot for the TFCMs of Matrimid ® and (b) 6FDA-6FpDA for temperatures
® ®and
Figure6.6.(a)
Figure (a)Arrhenius
Arrheniusplot
plotfor
forthe
theTFCMs
TFCMsofofMatrimid
Matrimid and(b)
(b)6FDA-6FpDA
6FDA-6FpDAfor
fortemperatures
temperatures
between 30 and 266 °C.
between3030and
between 266◦ C.
and266 °C.

InFigure
InIn Figure 7 the
7 the selectivity
selectivity of Hofof/CO
H2/CO
over 2 over the temperature for the Matrimid
the temperature for thefor
Matrimid
® and the 6FDA-
® and the 6FDA-6FpDA
Figure 7 the selectivity 2 H22/CO 2 over the temperature the Matrimid ® and the 6FDA-
6FpDA
TFCM are TFCM are With
presented. presented. Withtemperature,
increasing increasing temperature,
H /CO H2/CO
selectivity 2 selectivity increased. The
increased. The selectivity of
6FpDA TFCM are presented. With increasing temperature, 2 2 H2/CO2 selectivity increased. The
selectivity
the thick-film of the thick-film membranes was the highest in both polymers. Between◦ 30 and 80 °C, the
selectivity of membranes
the thick-filmwas the highest
membranes was inthe
both polymers.
highest Between
in both 30 and
polymers. 80 C,30the
Between andselectivity
80 °C, the
selectivity
followed followed
thefollowed
same trendthe same trend for all membranes.
selectivity the for
same all trend
membranes.
for all membranes.

Figure 7. (a) The selectivity of H2 /CO2 (-) over the temperature (◦ C) in Matrimid ® and (b) in
Figure 7. (a) The selectivity of H2/CO2 (-) over the temperature (°C) in Matrimid®® and (b) in 6FDA-
Figure 7. (a) for
6FDA-6FpDA Thedifferent
selectivity of H2/COand
membranes 2 (-) measurement
over the temperature
methods.(°C) in Matrimid and (b) in 6FDA-
6FpDA for different membranes and measurement methods.
6FpDA for different membranes and measurement methods.

4. Conclusions and Outlook

4. Conclusions and Outlook
A new highly thermally and chemically stable multilayer system for gas separation applications
A new highly thermally and chemically stable multilayer system for gas separation applications
at elevated temperatures was introduced. The system was composed of four different layers: non-
at elevated temperatures was introduced. The system was composed of four different layers: non-
woven support, polyphenylene sulfide (PPS); polybenzimidazole (PBI) as polymeric porous support
Membranes 2019, 9, 51 11 of 13

4. Conclusions and Outlook

A new highly thermally and chemically stable multilayer system for gas separation applications at
elevated temperatures was introduced. The system was composed of four different layers: non-woven
support, polyphenylene sulfide (PPS); polybenzimidazole (PBI) as polymeric porous support structure;
two different polyimides—Matrimid® or 6FDA-6FpDA—as selective layers; and Teflon® AF 2400 as
an external protective layer. The selective layers were successfully deposited as thin layers (<1 µm) on
top of the porous PBI support.
These thin-film composite membrane (TFCM) systems showed high thermal stability and
promising results for the separation H2 /CO2 at elevated temperatures. The separation properties of
the materials characterized in different thicknesses and by several techniques were compared. This
multilayer approach showed thermal stability for temperatures up to 270 ◦ C.
This type of highly thermally resistant polymeric membranes opens opportunities for application
in integrated processes operated at elevated temperatures, such as membrane reactors for the water-gas
shift reaction in order to maximize H2 yield.
Nevertheless, more efforts should be made toward the optimization of the thickness of the selective
and protective layers; the stability of the non-woven support (which in this case was an important
limitation); and new thermally resistant and highly selective polymers need to be tested under these
conditions. Furthermore, the multicomponent permeation performance of this new type of TFCM
needs to be further investigated.

Author Contributions: A.T., S.E. (Sonia Escolástico), S.S., J.M.S., and T.B. conceived of the idea; F.W., S.E.
(Sara Escorihuela), and A.D. designed, performed, and/or evaluated the experiments; A.T., S.E. (Sonia Escolástico),
S.S., J.M.S., and T.B. assisted in the evaluations of the experiments; F.W. and S.E. (Sara Escorihuela) wrote the
paper, while all authors contributed to the scientific discussion, revision, and finalization of the manuscript.
Funding: This work was financially supported by the project “New reactor technologies for chemical
and biochemical synthesis processes” (“Neue Reaktortechnologien für Chemische und Biochemische
Syntheseverfahren”, FKZ: LFF FV 43), funded by the City of Hamburg (Freie und Hansestadt Hamburg,
Behörde für Wissenschaft, Forschung und Gleichstellung), Germany, the Spanish Government (SEV-2016-0683,
SVP-2014-068356, Project ENE2014-57651-R and IJCI-2016-28330 grants), and Generalitat Valenciana
(PROMETEO/2018/006 grant).
Acknowledgments: The authors thank Silvio Neumann for thermal analysis experiments, Clarissa Abetz and
Anke-Lisa Höhme for the scanning electron microscopy experiments, and the microscopy service at Universitat
Politècnica de València (UPV) for the FIB and FE-SEM images.
Conflicts of Interest: The authors declare no conflict of interest.

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