Arabian Journal for Science and Engineering

https://doi.org/10.1007/s13369-023-08405-4

RESEARCH ARTICLE-CHEMICAL ENGINEERING

Poly(4-Methyl-1-Pentene) (PMP) with Nano Fumed Silica as Filler

for CO2 /N2 Gas Separation
Muhd Izzudin Fikry Zainuddin1 · Abdul Latif Ahmad1 · Reasmyraj R. Subramaniam1

Received: 15 March 2023 / Accepted: 8 October 2023

© King Fahd University of Petroleum & Minerals 2023

Abstract
Carbon dioxide (CO2 ) separation with membrane technology has become the focus of researchers over the past decades due to
its lower energy consumption and cheaper alternative. Mixed matrix membrane (MMM) of poly(4-methyl-1-pentene) (PMP)
with nano fumed silica particles was studied to determine the feasibility of using MMM to separate CO2 from nitrogen (N2 )
gas. The critical concentration of PMP (7 wt%) was utilized to form the membrane in this study in order to ensure the polymer
chain entanglement occurs to form a dense structure. Agglomeration of particle can be observed on the surface with scanning
electron microscopy (SEM) imaging with 10 and 15 wt% of nano fumed silica loading in PMP matrix. This observation is
further confirmed with energy-dispersive X-ray (EDX) mapping across the cross-sectional area which shows clustered nano
fumed silica particle with loading of 10 and 15 wt%. With 7.5 wt% filler loading and at 1 bar, the MMM seems to give the
best gas permeance performance with CO2 permeance of 4.62 GPU (100.54 Barrer) and N2 permeance of 0.20 GPU (4.31
Barrer) which makes the highest ideal selectivity to be about 23, which was the highest ideal selectivity achieved in this study.
Meanwhile, when the pressure was increased from 1 to 7 bar, the CO2 permeability increased almost linearly followed by a
steady decline in CO2 /N2 ideal selectivity.

Keywords Mixed matrix membrane · Nano fumed silica · Carbon dioxide separation · Polymeric membrane

1 Introduction (CA), perfluoropolymer, polyimide (PI) and Pebax-1657 are

among the polymers that are considered to be CO2 philic
Due to the obvious growing worry about climate change, [5]. However, the performance of pristine polymeric mem-
reducing greenhouse gas emissions, which are mostly made brane is known to be limited by the famous Robeson’s upper
up of CO2 , has gotten a lot of attention in recent years [1]. In bound [6]. As such, the combination of polymeric material
2018, the global CO2 concentration reached an all-time high with dispersed inorganic filler to form mixed matrix mem-
which is 407.8 ppm [2]. Fossil fuels, natural gas, petrochem- brane (MMM) with these polymers are simple yet effective
icals, power plants, and coal resources may all be considered procedure to overcome this boundary. MMM consists of a
important emitters of harmful greenhouse gases into the polymer as the continuous matrix phase, whereas the inor-
environment [3]. Current technologies such as cryogenic dis- ganic filler serves as the dispersed phase.
tillation, pressure-swing adsorption and chemical absorption Metal oxides are among common non-porous inorganic
requires high energy consumption and involves high cost of filler that are utilized to form MMM due to their easily avail-
operation. Membrane is seen as an interesting alternative able resources. Momeni and Pakizeh [7] fabricated MMM
for CO2 capture and storage application due to their sim- from PSf and magnesium oxide (MgO) for gas separation
ple process as well as requiring smaller carbon footprint [4]. study, in which they discovered that with increased filler con-
Polyethersulfone (PES), polysulfone (PSf), cellulose acetate tent, the gas permeability was observed to increase which
was ascribed to increased free volume content while the gas
selectivity reduced due to the agglomeration of the nanopar-
B Abdul Latif Ahmad
[email protected] ticle between the polymer matrix as observed by SEM. Molki
et al. [8] developed MMM consisting of polyurethane (PU)
1 School of Chemical Engineering, Universiti Sains Malaysia with nickle oxide (NiO) as the filler. According to them,
Engineering Campus, 14300 Nibong Tebal, Pulau Pinang,
the presence of NiO2 changed the crystalline structure of
Malaysia

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PU matrix. The optimal loading obtained in their study was 2 Materials and Methods
only 1 wt% of NiO loading while increasing the NiO load-
ing further reduced the gas permeability which was ascribed 2.1 Chemicals and Reagents
to the rigidification of polymer chain around the polymer
matrix–filler interface. Furthermore, it was observed that NiO Medium molecular weight of poly(4-methyl-1-pentene)
nanoparticle and CO2 exhibit Lewis’ acid–base interaction in (PMP) beads purchased from Sigma-Aldrich (USA) was
the MMM in addition to interaction between the polar –OH used as the polymer material to fabricate the membrane.
group on the surface of the hydrolyzed NiO nanoparticles. Reagent grade cyclohexane was purchased from Merck
Sheikh et al. [9] used ZnO as filler in Pebax-1657 in which (Germany) and used as solvent to dissolve PMP beads.
CO2 permeability was observed to increase with the incor- Nano fumed silica (SiO2 ) (BET surface area  120 m2 /g,
poration of ZnO filler as the presence of non-porous ZnO hydrophobic − 120°, particle size  7–40 nm) was pur-
altered the polymer chain packing thus increasing the free chased from Aladdin Chemicals Co. Ltd. (Shanghai, China)
fractional volume. Ahn et al. [10] discovered that increasing and used as the inorganic filler as dispersed phase in PMP for
the volume fraction of silica inside PSf membrane matrix the MMM fabrication. High gas purity cylinder of CO2 and
increases the permeability of the gases as a function of sil- N2 were purchased from local company, Alpha Gas Solu-
ica loading with reducing CO2 /CH4 selectivity that shows tion Sdn. Bhd. (Malaysia). All the purchased materials were
the trade-off pattern of Robeson’s upper bound, which was obtained in reagent grade purities and were used as received
attributed to the presence of voidage in between the PSf/silica without any modification or purification unless stated other-
interface of the MMM. Mesoporous silica was prepared by wise.
Zornoza et al. [11] that was embedded in PI Matrimid® 5218
for gas separation application. The fabricated MMM was 2.2 Fabrication of Pristine PMP Dense Membrane
subjected to binary CO2 /N2 mixed gas permeation to gauge
the performance of the MMM. Based on their findings, the Fabrication of dense PMP membrane with solvent evapora-
optimum loading was obtained at 8 wt% loading of calcined tion method was adopted from previously published literature
mesoporous silica. When the loading was further increased with slight modification [22]. One of the challenge in PMP
to 16 wt% reduced the gas pair selectivity due to the small membrane fabrication is the limitation of its solubility.
non-selective voids formed between the PI/silica interface, Hence, the PMP beads can be dissolved by only a hand-
although severe agglomeration of the filler was not observed ful of solvent. Beck [18] has listed out the list of solvents
in their studies. that can solvate PMP beads, however most of it requires high
Poly(4-methyl-1-pentene) (PMP) or its commercial name temperature (> 100 °C) to properly dissolve the PMP beads.
TPX is a highly crystalline glassy polymer with high free Only a handful of solvent that can dissolve the PMP beads
fractional volume having unique properties and high melting at temperature lower than 100 °C. Among them, cyclohex-
point [12–14]. It is typically used as extracorporeal mem- ane is shown to have the highest approximate solubility to
brane oxygenator (EMCO) due to its good O2 /N2 selectivity PMP compared to other solvents. Therefore, cyclohexane is
[15–17]. However, the main drawback is that it have limited chosen as the solvent to dissolve PMP in this study. Polymer
solubility in most solvents [18, 19]. It is also an interest- solution consisting of 2 to 9 wt% of PMP in cyclohexane was
ing membrane to be studied for CO2 gas separation due made by continuously stirring the dope solution in a Schott
to its high free volume. Recently, Wang et al. [20] con- bottle overnight with magnetic stirrer at 60 °C to obtain a
ducted a molecular dynamic simulation on the separation homogenously mixed dope solution. The Schott bottle was
characteristic of PMP membrane for CO2 /N2 gas separation sealed during the mixing. The polymer solution was then
where the separation factor is reported to be 4.83 at 298 K. degassed for about 30 min at 60 °C in an ultrasonic bath
Nematollahi et al. [3] prepared PMP/alumina mixed matrix to eliminate any bubbles formed in the dope. The degassing
membrane which showed significant permeability improve- of the dope was carried out at 60 °C to prevent the solidifi-
ment with increasing filler concentration. Abedini et al. [21] cation of the dope solution as the dope solution will lose its
incorporated copper benzene-1,3,5-tricarboxylate (CuBTC) solubility and become turbid when the temperature gradually
in the form of nanosheet into azide-crosslinked PMP mem- dropped to room temperature [23]. Additionally, 30 min time
brane which shows improved CO2 /H2 separation selectivity. was sufficient for the bubble to be completely degassed from
In this study, we incorporated a commercially available nano the dope solution. The dope solution was casted immediately
fumed silica particle into PMP membrane matrix utilizing after degassing using an automatic film applicator with pre-
solvent evaporation method for CO2 /N2 separation applica- determined thickness of 400 µm measured using Gardner’s
tion at various filler loading and upstream pressure which knife. The membrane was casted at a temperature of 20 °C
is yet to be exclusively reported for CO2 /N2 gas separation with relative humidity of 68%. After that, the casted polymer
application. solution was exposed to the air overnight at room temperature

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for solvent evaporation process. The membrane formed was membrane. The membranes were freeze fractured with liq-
immersed in distilled water, then manually peeled off from uid nitrogen prior to SEM observation. Fourier transform
the glass substrate, and washed again with distilled water sev- infrared attenuated total reflectance (FTIR–ATR) (Perkin
eral times and dried in a vacuum oven at 70 °C to eliminate Elmer) analysis was conducted onto both pristine PMP and
any leftover solvent that may remain in the membrane. MMM membrane samples to study the chemical bonding
presence in the fabricated membrane.
2.3 Fabrication of PMP MMM with Nano Fumed
Silica as Filler 2.5 2.5 Gas Permeation Test

For MMM fabrication, priming method was used to enhance Gas permeation test were carried out with bubble flow
the filler dispersion inside polymer matrix [24]. A precal- method using a permeation cell and pure gases of CO2 and
culated amount of PMP was dissolved in a Schott bottle N2 at room temperature [25]. A circular membrane cell with
overnight at 60 °C until a homogeneous solution was formed. effective permeation area of 3.142 cm2 was used for the gas
After overnight, a predetermined amount of silica (based on permeation experiment. The upstream pressure of the pure
dry polymer mass) was dispersed in cyclohexane solution gas was varied at 1,3,5 and 7 bar gauge, while the permeate
in a separate beaker and sonicated with ultrasonic bath for side was exposed to atmospheric pressure. Bubble flow meter
30 min to disperse the silica uniformly. Then, the cyclohexane was used to measure the flow rate of the permeate gas. The
with the silica nanoparticles suspension was poured into the experimental set up is shown in Fig. 2. The permeation rate
Schott bottle containing homogeneously mixed PMP dope was calculated by the following formula [26]:
solution under stirring condition at 60 °C and left for another
overnight to ensure uniform dispersion of silica nanoparticle P Vi
 (2)
to obtain the desired final mixture solution The loading of l P At
the nano fumed silica is varied at 0 wt% (PMP_0), 2 wt%
where P/l is the pressure-normalized flux of pure gas, or also
(PMP_2), 5 wt% (PMP_5), 7.5 wt% (PMP_7.5), 10 wt%
known as permeance in gas permeance unit (GPU) (1 GPU
(PMP_7.5), and 15 wt% (PMP_15) in this study. Similarly,
 1 × 10−6 cm3 (STP)/cm2 ·s·cmHg), V i is the volume dis-
after overnight stirring, the homogeneous dope mixture was
placed by the bubble during gas permeance test (cm3 ), ΔP is
sonicated at 60 °C for about 30 min to remove any trapped
the transmembrane pressure between the feed and permeate
bubble formations. The dope solution was casted using auto-
side (cmHg), A is the effective permeation area (cm2 ), t is
matic film applicator immediately at 20 °C with relative
the time taken for the volume of gas collected in the perme-
humidity of 68% using Gardner’s knife with a predefined
ation test (s). í is the membrane dense layer thickness (cm).
thickness of 400 µm on a glass plate. The membrane was
The ideal selectivity (unitless) of the membrane can then be
left to open air overnight to allow complete solvent evapo-
obtained by the ratio of individual gas permeance obtained
ration. Then, the MMM was peeled off from the glass plate,
from Eq. 2:
washed with distilled water several time, and dried with a
vacuum oven at 70 °C to remove residual solvent inside the 
Pi Pj
PMP/silica MMM. The silica content to form MMM was αi, j  (3)
calculated from Eq. (1). Schematic presentation of the mem- li lj
branes preparation is shown in Fig. 1.
where Pi /l i is the permeance of gas i, Pj /l j is the permeance
of gas j. The ideal selectivity is defined by α i,j which means
Silica(g)
Silica(wt%)  (1) the ideal selectivity of membrane of gas i to compared to gas
DryPMP(g) + Silica(g) j that represent the ratio of the permeance of the individual
species.

2.4 Membrane Characterization

3 Results and Discussion
The viscosity of the dope solutions was measured using
viscometer at 60 °C. The membrane sample cross section 3.1 Formation of Dense PMP Membrane
for pristine PMP and PMP MMM membrane was observed
by using scanning electron microscopy (SEM) imaging In this study, flat sheet PMP membrane was fabricated by
(TM3000, Hitachi) to study the surface and cross-sectional using solvent casting method at 20 °C and 68% of rela-
morphology of the membrane sample. ImageJ software was tive humidity. Cyclohexane is a volatile solvent. As such,
used to measure the thickness of the skin layer of the as the PMP solution is exposed to air, the cyclohexane will

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Fig. 1 Schematic representation of membrane fabrication process. Image of hot plate stirrer is made by Freepik, image of beaker is made
a PMP solution preparation b Nano fumed silica suspension. For pristine by Premium taken from flaticon.com
PMP membrane, nano fumed silica suspension preparation is neglected.

Fig. 2 Gas permeation test rig set up for gas permeation experiment

diffuse out from the PMP solution mixture forming a poly- to promote formation of dense and defect free membrane,
mer rich phase where the PMP polymer where the polymer particularly for gas separation application [29]. Besides, the
has sufficient time to aggregate together forming dense skin viscosity of the solution also plays a role of ensuring stability
layer. Previous study shows that 5 wt% of PMP exhibit good of the MMM dope suspension [30]. It is important to note
ideal selectivity [22]. However, in this study, considering that that the viscosity of polymer solution is a function of the
incorporation of inorganic filler into the polymer solution will polymer concentration. Dry phase inversion through solvent
disrupt the polymer chain packing [27, 28], the implemen- evaporation process is considerably slow, thus low solution
tation of critical concentration concept is crucial in order viscosity could lead to sedimentation of the inorganic particle

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1600

1400

1200

1000
Viscosity (cP)

800

600

400

200

0
2 3 4 5 6 7 8 9
PMP (wt.%)

Fig. 3 Graph of viscosity as a function of polymer concentration and its critical concentration

due to gravitational pull as the dope viscosity is not suffi- differ much from the literature, as such we conclude that the
cient to allow the suspension of the inorganic particles during fabricated membrane was free from defects. Therefore, PMP
solvent evaporation process. The effect is more pronounced concentration of 7 wt% is chosen as the fixed concentration to
with increase inorganic filler loading [31, 32]. High poly- fabricate MMM with various silica loading. The comparison
mer concentration leads to high dope viscosity. Nevertheless, is shown in Table 1.
excessively high viscosity is also not necessary for flat sheet
membrane fabrication as high viscosity dope is normally uti-
lized in hollow fiber formation [33]. As such, the viscosity 3.2 Morphology of Dense Pristine and MMM PMP
of the polymer solution is measured at various concentration
ranging from 2 to 9 wt%. 7 wt% of PMP concentration were The surface and cross-sectional morphology of pristine and
chosen from the viscosity measurement with respect to poly- MMM PMP is shown in Fig. 4. In general, it can be observed
mer concentration as it is the critical concentration obtained that when the PMP solution is subjected to dry phase inver-
in this study by intersecting the two tangents on the viscosity sion at room temperature, it yields to the formation of
curve as shown in Fig. 3. The critical concentration of poly- membrane with a fully dense structure. The cross section
mer refers to the significant chain entanglement between the of MMM showed a dense structure too and no defect were
polymer chain which is crucial in the formation of dense observed in the images. The thickness of the membranes mea-
skin layer Higher polymer concentration solutions beyond sured are almost similar for all 5 membranes based on the
the critical concentration are usually difficult to fabricate at SEM images. To further clarify this, the average thickness of
room temperature. Moreover, the resulting membrane would the MMMs was measured from SEM images at three different
be more rigid and thick leading to low gas flux. As the poly- locations, as summarized in Table 2. Based on the data from
mer concentration exceeds its critical value, polymer chains the table, the average thickness of MMM ranges from 18.3
tend to form entanglements and tighter intermolecular chain to 21.75 µm. The thickness of pristine PMP membrane with
displacement which may shift polymer behavior from more concentration of 7 wt% is 18.19 µm which was lower com-
fluid-like to more solid-like [34–36]. pared to MMMs in this study. According to Pang et al. (2019)
The gas separation performance of the pristine dense PMP [39], MMM embedded with nanofiller was thicker compared
membrane were elucidated and compared with previously to pristine membrane. This corresponds with the finding in
established literature with our fabricated membrane to deter- this study where there is slight increment in PMP membrane’s
mine if the fabricated membrane experience any defect or not. thickness with the presence of nano fumed silica as the
The CO2 permeability and CO2 /N2 ideal selectivity does not filler. Regardless, the cross section of MMM PMP does not
shows any sign of nano fumed silica particle which could be

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Table 1 Performance comparison

of pristine dense PMP membrane Membrane Type Condition CO2 permeability α(CO2 /N2 ) Reference

PMP/PP (5 wt%) TFC 37 °C 2 kgf/cm2 ~ 14 GPU ~ 6.7 [17]

PMP (5 wt%) FS 35 °C 2 bar 97.2 Barrer 16.4 [21]
PMP (5 wt%) FS 25 °C 5 bar 76.46 Barrer 11.57 [22]
PMP (Commercial HF 25 °C 60.73 Barrera 7.4 [37]
Oxyplus)
PMP HF 23–25 °C 68.4 Barrer 12.7 [38]
PMP (7 wt%) FS 25 °C 3 Bar 63.67 Barrer 12.32 This work
a Thepermeability (Barrer) is calculated by multiplying the gas permeance value (GPU) with estimated skin
thickness of 0.1 µm

Table 2 Average thickness of fabricated pristine and MMM PMP the silica content is further increased to 10 wt% and 15 wt%,
respectively. Our finding is similar to study conducted by
Silica nanofillers concentration (wt%) Thickness of membrane
(µm) Shirvani et al. [40] in which they observed that the agglom-
eration of silica is more pronounced at higher concentration
0 18.19 in their polyurethane/polyvinyl alcohol membrane matrix.
2 18.12 At high filler concentration loading, the stronger filler–filler
5 21.23 interaction overcoming the filler–polymer interaction might
7.5 18.3 have led to the occurrence of the filler agglomeration, thus
forming non-selective voids which can detrimentally affect
10 21.75
the gas separation performance [41]. Evidently, sedimenta-
15 18.87
tion of nano fumed silica is not observed in this study as
observed by Jusoh et al. [32] which indicates that the dope
viscosity is sufficient to allow the suspension of inorganic
attributed to the small size of the particle which is not observ- filler during solvent evaporation process. As such, determin-
able due to the limited magnification. Therefore, the presence ing the optimum filler concentration is important to obtain
and distribution of the nano fumed silica is confirmed by EDX a finely dispersed filler inside a homogeneous membrane
mapping. Additionally, there are no observable pores from matrix to form defect free MMM. In this study, nano fumed
the surface morphology of both pristine and MMM PMP silica is finely dispersed throughout the PMP matrix up to
and the presence of nano fumed silica does not contribute 7.5 wt% loading, while clustered nano fumed silica can be
to any structural change of membrane surface morphology. observed when the loading is further increased.
However, for PMP containing 10 wt% silica, small white
dots as circled in yellow in the image shows aggregation
of the nano fumed silica on the surface of the membrane. 3.3 FTIR–ATR Analysis
The phenomenon is more significant 15 wt% of nano fumed
silica where the white spot formation is more pronounced The FTIR–ATR analysis of both pristine and MMM PMP
signaling the agglomeration of nano fumed silica to be sig- was conducted to elucidate the surface chemical bonding that
nificant. Additionally, pore-like structure also appeared on exist in the PMP, and PMP/silica membrane and the spectra
the surface of PMP membrane containing 15 wt% of silica. were recorded and merged together for the resulting mem-
Membrane with lower silica loading (< 5 wt%) shows no brane to elucidate the surface chemical bonding that exist in
sign of white spot which indicates good dispersion of nano the PMP membrane, as represented in Fig. 5. The highest
fumed silica inside the PMP polymer matrix. The EDX map- peak on the left side, which is at wavenumber of approx-
ping of the Si element (Fig. 4) across the cross-sectional imately 2950 cm−1 in the figure refers to the C–H alkane
area conform to the observation of the surface’s morphol- bond stretch of the PMP polymer, while the lower peak in
ogy. When the silica loading is lower than 5 wt%, the silicon the middle which ranges from 1360 to 1460 cm−1 indicates
(Si) element dispersed sparsely across the cross-sectional the C–H alkane bond stretch that refers to the methyl group
area without sign of clustered particles, meanwhile at 7.5 of the PMP polymer [22]. The spectra band at 1077 cm−1 and
wt% loading, Si element mapping shows denser dots across 435 cm−1 in the figure refers to the Si–O–Si group bond of the
the cross-sectional area owing to the increased filler content. nano fumed silica [42]. The height of the peak is increases for
Ultimately, the apparent cluster of nano fumed silica across a given region with increasing silica wt%. This means with
the cross-sectional area as circled in orange is observed when higher PMP/silica ratio, there is more silica nanoparticle that

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Fig. 4 Surface (1 500× Membrane Surface morphology Cross section Elemental mapping (Si)
magnification) and
PMP_0 N/A
cross-sectional (10 000×
magnification) morphology with
correspondent elemental EDX
mapping of silicon (Si) of
pristine and MMM PMP. The
inset of the surface morphology
shows the water CA obtained
from five average values. Yellow
circle shows the apparent PMP_2
clustered nano fumed silica on
the membrane’s surface, while
orange circle shows the apparent
clustered nano fumed silica of
cross-sectional area obtained by
EDX mapping

PMP_5

PMP_7.5

PMP_10

PMP_15

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Transmittance (a.u)
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Silica 2 wt.% 5 wt.% 7.5 wt.% 10 wt.% 15 wt.% Pristine PMP

Fig. 5 FTIR–ATR spectra of pristine and MMM PMP

will absorb the emitted light which will reduce the transmit- facilitating their diffusion [43] as compared to porous filler
tance reading. The FTIR–ATR analysis and EDX mapping where the presence of porous filler with suitable pore size
confirms that the nanofumed silica is successfully incorpo- will facilitate the gas transport through the pore itself, thus
rated into PMP during the MMM fabrication. governing the gas transport by molecular sieving properties
[44]. The highest ideal selectivity CO2 /N2 was obtained in
this study with 7.5 wt% loading of nano fumed silica content
3.4 Gas Separation Properties which is at 20.43 that correspond to about 66% improve-
ment as compared to pristine PMP membrane. Meanwhile,
3.4.1 Effect of Nano Fumed Silica Loading on MMM PMP the CO2 permeance increased from 3.52 GPU (63.67 Bar-
Membrane rer) for pristine PMP to 5.66 GPU (123.06 Barrer) with 7.5
wt% nano fumed silica content. The observed increase in
The effect of nano fumed silica loading on MMM PMP gas permeability could be due to the increase in free vol-
fabrication is further elucidated with pure gas separation per- ume content of the polymer matrix due to the disruption of
formance at 3 bar pressure and room temperature condition polymer chain packing with the presence of nano fumed sil-
which is shown in Fig. 6. Based on the trend, the gas perme- ica. The interaction between polymer matrix and filler, the
ance increase with increasing silica loading. For pristine PMP voidage at the intersection between polymer matrix and filler
membrane, the CO2 permeance is recorded to be at 3.50 GPU is formed, thus contributing to higher free volume formation
which is at the lowest reading as compared to the MMM fab- in the polymer matrix, which is accompanied by the increase
ricated. As the content of nano fumed silica loading in the in gas permeability. As shown in Table 3, the CO2 permeance
PMP matrix is increased from 0 to 7.5 wt%, the CO2 gas and permeability increment is more significant as compared
permeance shows an almost linear increment trend of CO2 to N2 gas, hence improving the ideal selectivity of CO2 /N2
gas permeance. However, a huge CO2 permeance jump was when the nano fumed silica is increased up to 7.5 wt%. This
observed when the nano fumed silica content is increased phenomenon can be ascribed to the smaller kinetic of CO2
up to 10 and 15 wt%. Meanwhile, the ideal selectivity of as compared to N2 gas. Additionally, CO2 has high con-
CO2 /N2 gas increases with respect to nano fumed silica load- densability and polarity compared to N2 gas. As such, the
ing up to 7.5 wt% before starting to decline at 10 and 15 wt% diffusivity of CO2 gas through the MMM improved better
loading. Silica is a non-porous particle. It is well accepted relative to N2 . Additionally, the nanoscale particle size of
that the presence of non-porous filler increases the free frac- the nano fumed silica used yield high polymer matrix–filler
tional volume of a glassy polymer, thus forming more free
path for gas penetrant to travel through the dense membrane

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350 25

300
20

250

15
CO2 (Barrer)

200

α(CO2/N2)
150
10

100

5
50

0 0
0 2 5 7.5 10 15
Silica content (wt.%)

Fig. 6 Gas separation performance of PMP with various nano fumed silica loading at 3 bar and room temperature

Table 3 Permeance (GPU) and permeability (Barrer) of PMP at various silica loading (P  3 bar, T  25 °C)

Membrane CO2 permeance CO2 permeability N2 permeance N2 permeability CO2 /N2 selectivity
(GPU) (Barrer) (GPU) (Barrer)

PMP_0 3.50 63.67 0.28 5.17 12.32

PMP_2 3.52 74.70 0.27 5.83 12.81
PMP_5 4.75 102.43 0.32 6.88 14.90
PMP_7.5 5.66 123.06 0.28 6.03 20.43
PMP_10 14.91 281.27 0.99 18.77 14.99
PMP_15 17.33 317.23 1.15 21.02 15.12

interfacial interaction, thus increasing the polymer matrix— to 15 wt%. It is typical that at high loading, agglomeration
filler contact. The presence of non-porous nanoparticle filler normally occurs due to the stronger filler–filler interaction
may act as a pore or capillary modifier or even forming thin exceeding the polymer matrix–filler interaction, thus form-
selective layer during MMM preparation. ing cluster of nanoparticle aggregates. This phenomenon is
However, a contrasting effect occurs when the nano fumed typically not favorable in MMM fabrication as they can form
silica loading is further increased to 10 and 15 wt%. It can be non-selective, highly permeable voids, thus affecting the gas
observed from both Fig. 6 and Table 3 that there is significant separation performance negatively. Due to the formation of
jump in gas permeance, and permeability accompanied with non-selective voids, both CO2 and N2 experienced similar
a drop of CO2 /N2 gas ideal selectivity as compared to MMM permeability increment thus no significant improvement of
PMP with 7.5 wt% nano fumed silica loading. From our find- CO2 /N2 is observed which is in line with SEM images obser-
ings, CO2 gas permeance increased from 5.66 GPU (123.06 vation in Fig. 4. The highest ideal selectivity is obtained for
Barrer) with 7.5 wt% filler loading to 14.91 GPU (281.27 MMM with loading of 7.5 wt% in this study. The MMM with
Barrer) at 10 wt% filler loading and further increase to 17.33 7.5 wt% is further subjected to various upstream pressure to
GPU (317.23 Barrer) at 15 wt% filler loading. Meanwhile the study the effect of operating pressure.
ideal CO2 /N2 selectivity dropped from 20.43 to 14.99 when
the filler loading is increased from 7.5 to 10 wt% and remain
relatively similar when the filler loading is further increased

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140 24

22
130

20
120
CO2 (Barrer)

18

α(CO2/N2)
110
16

100
14

90
12

80 10
1 3 5 7
Pressure (bar)

Fig. 7 CO2 permeability and CO2 /N2 selectivity as a function of upstream pressure for PMP_7.5

3.4.2 Effect of Pressure on MMM PMP Gas Separation 4 Conclusion

Performance
From this study, a MMM using nano fumed silica particle
The effect of feed pressure on gas separation performance with PMP matrix is successfully fabricated and tested for
PMP_7.5 was studied to determine its effect on the gas CO2 /N2 gas separation. 7 wt% of PMP membrane is chosen
permeability and ideal selectivity where the result is dis- to fabricate mixed matrix membrane with silica nanoparticles
played in Fig. 7. Based on this study, there is a steady as fillers because of the significant polymer chain entangle-
of CO2 permeance with respect to increase upstream pres- ment and to minimize the formation of unselective void with
sure with declining of CO2 /N2 gas ideal selectivity. With the inclusion of silica nanoparticle. Nano fumed silica is a
higher transmembrane pressure differences between the feed non-porous filler which disrupts the polymer chain packing
and permeate site, thus the driving force facilitating the gas of the polymer matrix, thus contributing to increased free
penetration through the membrane matrix is higher which fractional volume of the polymer which is reflected in the
constitutes to the increased CO2 permeability which is in line increased in gas permeability. Based on SEM images, the
with result observed by Hassanajili et al. [27] Nevertheless, nano fumed silica dispersed evenly throughout the mem-
our finding is in conflict with Nematollahi et al. [3], in which brane matrix up to 7.5 wt%, while apparently agglomeration
they observed that the increase in upstream pressure is also is observed when the loading is further increased. Based on
accompanied by increased CO2 /N2 ideal selectivity, which gas performance test, 7.5 wt% of nano fumed silica con-
is in contrast to our discovery. According to them, CO2 is a tent appears to exhibit the best gas separation performance
highly condensable gas and more polar as compared to N2 where the CO2 permeability is recorded to be 123.06 Barrer
thus CO2 induced better interaction with the polymer chain as with CO2 /N2 ideal selectivity of 20.43 which correspond to
compared to N2 which contributed to the increased CO2 /N2 93% and 66% improvement as compared to pristine PMP,
at elevated pressure. Additionally, membrane-softening phe- respectively. The CO2 increased significantly when the load-
nomenon also occurred with increased pressure. Although, ing is further increased to 10 and 15 wt% with reduced ideal
in this study, the gas permeability increment may also be CO2 /N2 selectivity due to the apparent agglomeration of nano
attributed to macroscopic defect that arise between poly- fumed silica. There is no sedimentation of nano fumed silica
mer matrix and filler and become more significant at higher observed in the PMP matrix in this study. Lastly, increasing
pressure, thus contributing to the reduction of CO2 /N2 ideal the upstream pressure shows increment in CO2 gas per-
selectivity. meability with reduction on ideal CO2 /N2 due to potential
membrane-softening phenomenon.

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Acknowledgements This work was supported by the Fundamental 12. Tsarkov, S.; Khotimskiy, V.; Budd, P.M.; Volkov, V.; Kukushkina,
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.026
Declarations 13. Wolińska-Grabczyk, A.; Jankowski, A.; Sekuła, R.; Kruczek, B.:
Separation of SF6 from binary mixtures with N2 using commercial
poly(4-methyl-1-pentene) films. Sep. Sci. Technol. 46, 1231–1240
Conflict of interest The authors declare that they have no known com-
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peting financial interests or personal relationships that could have
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