Separation Science and Technology

ISSN: 0149-6395 (Print) 1520-5754 (Online) Journal homepage: http://www.tandfonline.com/loi/lsst20

Modification of polycarbonate membrane by

polyethylene glycol for CO2/CH4 separation

Zahra Hamrahi & Ali Kargari

To cite this article: Zahra Hamrahi & Ali Kargari (2016): Modification of polycarbonate
membrane by polyethylene glycol for CO2/CH4 separation, Separation Science and Technology,
DOI: 10.1080/01496395.2016.1260143

To link to this article: http://dx.doi.org/10.1080/01496395.2016.1260143

Accepted author version posted online: 14

Nov 2016.

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Download by: [FU Berlin] Date: 18 November 2016, At: 10:50

Modification of polycarbonate membrane by
polyethylene glycol for CO2/CH4 separation
Zahra Hamrahi a, Ali Kargari b,∗
a
Young Researchers and Elite Club, Omidiyeh Branch, Islamic Azad University, P.O. Box 164,

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Omidiyeh, Iran.

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b
Membrane Processes Research Laboratory (MPRL), Department of Chemical Engineering,

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Amirkabir University of Technology (Tehran Polytechnic), Tehran, Iran.

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Abstract an
In this study, permeation of carbon dioxide (CO2) and methane (CH4) through the

polycarbonate/polyethylene glycol (PC/PEG) blend membrane was investigated. The effect of

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PEG content (0-5 wt.%) on the permeability and selectivity was studied. Permeability

measurements were carried out at pressures of 1-7 bar and at room temperature. The membranes
ed

were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy

(FTIR-ATR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential

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scanning calorimetry (DSC), and density measurement. The results revealed that the PC/PEG
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blends are miscible/partially miscible without considerable micro-phase separation. The effect of

PEG content and gas pressure on the diffusion and solubility of coefficients were also
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investigated and analyzed. It was concluded that the most influential parameter for the

permeation is the diffusion coefficient of the gases. The permeability and selectivity decrease as

∗
Corresponding author: Tel: +98 (21)66499066; fax: +98 (21)66405847,
E-mail: kargari@aut.ac.ir ; ali_kargari@yahoo.com

1
the operating pressure and PEG content is increased. Furthermore, the results showed that the

addition of 5 wt.% of PEG into PC increases the CO2/CH4 selectivity from 26.6±0.99 to

40.9±2.14 (more than 53%) at 1 bar.

Keywords: Membrane gas separation; Polycarbonate; Polyethylene glycol; CO2/CH4 separation;

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Permeability; Selectivity.

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1. Introduction

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Biogas or biomethane is expected to be the future source of energy. Biogas is produced by the
an
anaerobic digestion of the carbon containing natural substances such as carbohydrates, cellulosic

materials, hydrocarbons and organic wastes. Presently, sewage digesters and landfills are the
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main sources for biogas production. However, the raw biogases could not be used as fuel due to

the high amounts of acid gases such as CO2. The presence of the inert and acid gases
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considerably reduces the heating value and wastes the pipeline capacity [1]. The acid gases in the

vicinity of partial amounts of water can cause corrosion in the gas transport pipelines and other
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equipment [2]. These sour gases require treatment through the gas sweetening units to produce
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an acceptable natural gas for fueling and other applications [3]. Usually, the amount of CO2

should be decreased to less than 2 mol % [4].

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Removal of such high amounts of carbon dioxide from biogas is the most important challenge in

using biogas for industrial and domestic applications. Conventional methods such as absorption

by alkaline solutions (i.e. ethanol amines), adsorption on solid surfaces such as active carbon and

cryogenic distillation are currently used for treating the sour gases [5].

2
Recently, membrane separation technologies have been introduced as an efficient and clean

method for separation of different gases [6, 7]. Polymeric materials have been widely used for

membrane fabrication through the past decades because of ease of fabrication, availability, the

possibility of blending two or more polymers and/or tailoring new polymers for a specific

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separation application. Many researchers have been considered separation of carbon dioxide

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from different gaseous systems such as CO2/N2 and CO2/CH4 [8-18].

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Polycarbonates (PCs) are glassy thermoplastic polymers which have been widely used for

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industrial and domestic applications. The most known type of polycarbonates is “Bisphenol-A

polycarbonate” which is the product of reaction between Bisphenol-A and phosgene.

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The first effort in using PC as the membrane for gas separation dates back to the work of Norton

in 1963 [19]. He measured the permeability, diffusivity and solubility of some gases such as N2,
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O2, CO2, SF6, H2, H2O and also inert gases of He, Ar and Ne in the Lexan PC dense film. In

1972, Vieth and Eilenberg reported the results of sorption of CO2, CO and Ar gases in PC film
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and found that the sorption of the gases in PC obeyed the dual sorption mechanism. They

reported the dual sorption parameters and also the diffusion coefficients of the gases in the PC
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membrane [20, 21]. In 1976, Koros et al. investigated CO2 sorption and transport in PC
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membranes [22]. They showed that the permeability of CO2 in the PC membrane reduced as the

upstream pressure was increased from 1 to 23 atm. Moreover, they reported that the solubility of
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CO2 in the PC membrane increases as the feed pressure increases. In addition, Koros et al.

studied the sorption and transport of N2, CO2, CH4, He and Ar in the PC membrane using the

time-lag method and offered some colorations for sorption and transport parameters [23].

Wonders et al. showed that CO2 exposure history affects the sorption and transport properties of

3
the PC membrane. They related this to the plasticization effect of CO2 on the glassy structure of

PC [24]. Muruganandam et al., studied the gas sorption and transport in substituted

polycarbonates (tetra-methyl, tetra-chloro, and tetra-bromo substitutions onto the aromatic rings

of bisphenol-A polycarbonate). They found that tetra-methyl substitution increases the

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permeability by three to four folds while the tetra-bromo and tetra-chloro substitutions reduce the

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permeability with respect to the tetra-methyl substitution [25].

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Chen et al. studied the transport of O2 and N2 through pure PC and cobalt (III) acetyl acetonate

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containing PC membranes and showed an increase in oxygen permeability by this modification

[26]. In another work, Chen et al. found that selectivity and gas solubility increases when the PC
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membrane is treated with supercritical CO2 [27]. Şen studied the effect of adding 0.5 to 10 wt.%

of p-nitroaniline (pNA) as compatibilizer to the PC membrane and achieved a selectivity of 53.9

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for CO2/N2 [28]. Acharya et al. studied the effect of temperature on permeation of H2 and CO2

through a dense PC membrane and found that the permeabilities and diffusivities increased with
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temperature while the solubilities decreased [29]. Kim and Lee [30] prepared porous PC

membranes by introducing PEG into the PC followed by phase inversion under high pressure
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supercritical CO2. They studied the effect of porosity on the tearing stress of the porous PC
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membranes. Sridhar [31] prepared sulfonated PC membranes for separation of binary gas

mixtures of CO2 and CH4 and showed that sulfonated PC membranes have a lower permeability
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and higher selectivity than the pristine PC. Iqbal [32] prepared asymmetric PC membranes for

gas separation and studied the solvent effect on the performance of the asymmetric membranes.

They used different solvents such as dichloromethane, chloroform and different non-solvents

such as ethanol, propanol and butanol. It was observed that the evaporation rate of solvent and

4
non-solvent has a severe effect on the membrane morphology and CO2/CH4 separation

performance.

In 2012, the Research Triangle International Institute (RTII) introduced a new type of PC hollow

fiber membrane provided by Generon, named “High-Flux Next Generation” polycarbonate

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membranes for CO2 capture from power plant flue gases. This membrane has shown a CO2

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permeability and CO2/N2 separation selectivity as 22 and 47, respectively which shows a

considerable improvement in comparison with the standard PC membranes (CO2 permeability of

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4.5-5.0 and CO2/N2 separation selectivity of 29) [33].

Modification of polymeric membranes by polyethers for improving CO2 permeability and/or

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selectivity via the interaction of the polar CO2 and etheric oxygen atom has been an attractive

area of research in recent years. Polyethylene glycols (PEGs) are a series of polyethers that have
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been used as pore former in porous membranes and modifier in gas separation membranes such

as CO2 separation membranes [29, 34-36]. The main flexible chain properties of PEGs have
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made them suitable for gas separation due to the better diffusivity of large penetrants. Generally,
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PEG is one of the plasticizers that are often employed for controlling the total free volume and

increasing the chain mobility of the backbone polymer [35, 37].

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The above literature survey shows that modification of the PC gas separation dense membrane
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by a polyether has not been carried out up to now, and so, it is a novel work. It is expected that

blending the PC polymer with a low molecular weight polyethylene glycol (PEG), enhances the

CO2/CH4 separation performance. Therefore, in this study, the fabrication and characterization of

flat sheet blend membranes composed of PC and PEG (with molecular weight of 300 g/mole) for

5
CO2/CH4 separation is investigated. The effect of PEG content (in the range of 0-5 wt.%) and

operating pressure (1-7 bar) on the permeability, selectivity, diffusivity and solubility

coefficients of CO2 and CH4 is considered. The DSC, XRD, FTIR, SEM analyses and density

measurement along with gas permeation tests are used for characterization of the prepared

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membranes.

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2. Experimental

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2.1. Materials an
Polycarbonate (PC) resin with a glass transition temperature (Tg) of 135 °C and weight averaged

molecular weight (Mw) of 21000 g/mole was supplied by Khuzestan Petrochemical Co.,
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Mahshahr, Iran. Polyethylene glycol (PEG) with a molecular weight of 300 was acquired from

Kimiagaran-e-Emrooz Chemical Industries Co., Arak, Iran. Chloroform (Dr. Mojallali Chemical
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Laboratories Co., Tehran, Iran) with 99% purity was used as the solvent. CO2 and CH4 with a

purity of 99.999 and 99.995 %, respectively, were purchased from Technical Gases Ltd. supplied
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by Oxygen Yaran Co., Mahshahr, Iran.

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2.2. Preparation of membranes

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The PC resin was dried in an oven at 110°C for 12 hours before use. Then, polymer solutions

were prepared by dissolution of predetermined quantities of the PC and PEG-300 (totally 5

wt.%) in chloroform (95 wt.%) at room temperature to make polymeric membranes containing 0,

1, 3, and 5 wt.% of PEG-300. The solutions were stirred for about 5 h and then allowed for

6
degassing for about 30 minutes. The degassed solutions were then casted onto cleaned and dried

glass plates by a casting knife at room temperature and the resulted polymeric films were dried in

an oven at 40 °C for 12 h. The final thickness of the prepared membranes was about 24±1 µm

and a circular coupon with an active diameter of 47 mm was used for the permeation

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experiments.

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2.3 Gas permeability measurements

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The gas permeabilities were measured by the known time-lag method (constant-volume method).

In this method, the pressure changes in the downstream membrane chamber are measured by a
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precise pressure transducer.

All the membrane samples were tested at a temperature of ~25 °C and feed pressures in the range
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of 1-7 bar. The steady rate of pressure increase (dp/dt) at the permeate side was measured by a

precision pressure transmitter (type 691, Huba Control, Würenlos, Switzerland) and used to
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calculate the permeability using equation (1):

273.15 × 1010 Vl  dp 
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P=   (1)
AT(p0 × 76 )  dt 
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where P is the gas permeability in Barrer (1 Barrer = 1 cm3 (STP) cm/cm2cmHg s), V is the dead-

volume of the downstream chamber (cm3), l is the membrane thickness (cm), p0 is the feed
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pressure (atm), and dp/dt is the steady rate of pressure increase in the downstream side (atm/s), A

is the effective membrane area (cm2) and T is the absolute temperature (K). To ensure the

accuracy of the data acquisitions, each measurement was replicated on the three different

7
membrane samples with the same composition and the reported value is the arithmetic mean of

the three samples.

2.4. Diffusivity, solubility and selectivity

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The thermodynamic properties of CO2 and CH4 are shown in Table 1 [1]. The diffusivity,

solubility and also the ideal separation factor (selectivity) of CO2 over CH4 were determined

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through the gas permeability experiments. The diffusivity coefficients (D) of the gases across the

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membranes were determined from the time-lag measurements [38]. Generally, the diffusion

coefficients were calculated according to Eq. (2):

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l2
D= (2)
6
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Where l and θ are the membrane thickness and the time-lag (s), respectively. The solubility

coefficient (S) was determined by using the diffusion coefficient and gas permeability results.
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Usually, the solubility coefficient is calculated according to Eq. (3):

P
S= (3)
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where P is the gas permeability, D is the diffusivity coefficient (cm2/s) and S is the solubility
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(cm3(STP)/cm3.cmHg) [34].

In addition, the selectivity of the two components, , was calculated by dividing the
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( CO2 / CH 4 )

respected permeabilities in the same conditions by Eq.(4).

PCO 2
( CO2 / CH 4 ) = (4)
PCH 4

Where PCO2 and PCH4 are the permeabilities of CO2 and CH4 in the same condition, respectively.

8
2.5. FTIR

Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR) was performed

on the membrane samples using a Thermo Scientific™ Nicolet iS10, Smart™ iTX model

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(Thermo Fisher Scientific Inc., USA) in the range of 600–4000 cm-1. Smart™ iTX is a single-

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bounce ATR (attenuated total reflectance) device that accommodates interchangeable

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germanium (Ge), diamond, zinc selenide (ZnSe) and crystal plates. It is used in order to optimize

the FT-IR spectrometer’s material characterization capabilities when analyzing liquid or solid

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samples. an
2.6. Scanning electron microscopy (SEM)
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Surface and cross sectional images of the membranes were investigated by scanning electron

microscopy (SEM) (model LEO 1400, Carl Zeiss, Oberkochen, Germany). The samples were
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fractured in liquid nitrogen and then were gold coated by a BAL-TEC SCD 005 sputter coater

(BAL-TEC AG, Balzers, Liechtenstein) before performing the scanning.

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2.7. Differential scanning calorimetry (DSC)

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Thermal behavior of the pure PC and PC/PEG blend membranes was studied by a differential
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scanning calorimeter (DSC, Model 200-F3, Netzsch, Germany). Each scan was performed in the

range of -100 to 250 °C with a heating rate of 10 °C/min. The cooling mode was applied using

liquid nitrogen and the heating was performed under nitrogen atmosphere to prevent any possible

oxidation reactions.

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2.8. XRD

The X-ray diffraction (XRD) patterns for analyzing the crystallinity of the polymeric membranes

was obtained by a very high resolution diffraction system (Intel Equinox 3000, France) wide-

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angle X-ray diffractometer. The scan range was varied from 2θ=5º to 118º with a step increment

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of 0.0310º s-1. The measurements were performed at room temperature by monochromatic

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radiation of α-rays emitted by CuKα radiation (λ=1.54060 Å), at 40 kV and 40 mA.

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2.9. Density measurement an
Density of the membranes were determined by a density gradient column of water-CaCl2

solution at 25 ºC. Under this condition, the density of samples in the range of 0.9971 (pure
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water) to 1.4628 (45 wt.% in water) could be determined.

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3. Results and discussion

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3.1. Characteristics of the membranes

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3.1.1. FTIR-ATR
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Fourier transform infrared spectroscopy-attenuated total reflectance spectroscopy (FTIR-ATR)

spectrums for the prepared membranes are shown in Fig. 1. In the polyethylene glycol (PEG)

spectrum, a broad absorption band around 3400 cm−1 is attributed to stretching vibration

hydroxyl (O‒H) groups. The band around 1500 cm−1 is associated to H‒O‒H bending vibrations

10
of adsorbed water molecules [35, 39, 40]. A strong and sharp band at ~2850 cm−1 is referred to

C‒H symmetric/asymmetric stretching vibrations in the polyethylene segment, while the bands at

around 1450 and 1350 cm−1 are respectively assigned to rocking and bending vibrations (C‒H

deformation). In addition, a large and sharp band at ~1100 cm−1 is related to asymmetric

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stretching vibrations of C-O-C in PEG (known as the characteristic absorption band of PEG),

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while the three slim shorter bands at 933, 883, and 827 cm−1 are attributed to the symmetric

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stretching vibrations of C-O-C [41].

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For pure polycarbonate (PC), a major absorption band of the carbonyl groups (C=O stretching)

of polymer occurred at around 1770 cm-1 [42].

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The band (1770 cm-1) is shifted to shorter frequency upon the addition of 1 wt.% PEG that

indicates a hydrogen bonding between the carbonyl group of polymer and the terminal ‒OH
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group of PEG [43]. The existence and strength of hydrogen bonding can be employed as a

criterion for miscibility at low PEG loading [44, 45].

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In the case of 3 and 5 wt.% PEG-loaded PC membranes, no new absorption band appears despite

what exists in the pure PC. However, a characteristic carbonyl group of PC at ~1770 cm-1
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becomes strengthened. This phenomenon occurred due to the superposition of PEG and PC
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carbonyl groups. Therefore, it can be concluded that a degree of phase separation or

immiscibility of the blend might occur.

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11
3.1.2. SEM

The SEM images (surface and cross section) of the pure PC and PC/PEG blend membranes are

shown in Fig. 2a to 2h. Figs. 2(a) and (b) show the cross section and top surface images of the

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pristine PC membrane, respectively. A homogenous morphology without visible cracks or voids

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is observed that confirms a dense structure of the membrane both for the cross section and top

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surface of the PC dense membrane. Figs. 2(c) to (h) show the SEM images of the cross sections

and top surfaces of the PC/PEG blend membranes corresponding to 1, 3 and 5 wt.% PEG content

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samples. Similar to the pristine PC membrane, a dense structure is observed for the PC/PEG

blend membranes in Figs. 2(c) to (h). Only for the sample containing 5 wt.% PEG, some white
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spots are observed in the cross section image that could be the separated small droplets of PEG.
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All cross section/top surface images show no holes or cracks that confirm the dense structure of

the membranes wherein the transport of species is dominated by the solution-diffusion

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mechanism.

3.1.3. DSC
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The influences of PEG content on the thermal behavior of the PC/PEG blends are shown in Fig.
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3. The glass transition temperatures (Tg) of the membranes were shown in Fig. 3. As observed,
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the temperature corresponds to the midpoint location of the deflection in each DSC thermogram

considered as Tg of the sample. It reduces from 135 to 105 °C for the pristine PC to the PC/PEG

blend membrane containing 5 wt.% PEG, respectively. The glass transition temperature for

PC/PEG blends with 1 and 3 wt. % of PEG was obtained as 126 and 117 °C, respectively.

12
The glass transition of PEG-300 is -73.6°C [46], but it could not be observed in any of the

thermograms in Fig. 3. A small, sharp peak is observed in the thermograms of the membranes

containing 3 and 5 wt.% PEG-300 at 48 and 41°C, respectively, which can be due to the

impurities existing in the PEG. However, the decrease in glass transitions of the blend

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membranes with the increase in PEG content is attributed to the effect of low molecular weights,

rubbery PEGs on the glassy behavior of the PC polymer [35, 38]. The PEGs have very low glass

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transition temperatures and the interaction of PEG, even at low concentrations, with the

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polycarbonate matrix causes a considerable decrease in the glass transition temperature [28]. It is

worth quoting that a third, broad peak was observed for the PC/PEG blend samples in the range
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of 177-196 °C which is shifted to lower values by increasing the PEG content. This peak may be

due to evaporation or thermal degradation of PEG [47]. Generally, it could be concluded that
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PC/PEG-300 blends are miscible (or partially immiscible) without considerable micro-phase

separation in this range of PEG content.

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2.8. XRD

The X-ray diffraction (XRD) patterns for the various fabricated membranes are shown in Fig. 4.
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Broad peaks are observed for all the samples. The center of the broad peak in the X-ray patterns
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is attributed to intersegmental interference and shows the average intersegmental spacing which

is called d-spacing which could be calculated with Bragg’s equation (nλ=2d sinθ). Table 2 shows
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the numerical results of the XRD analysis of the samples. The XRD pattern for the pristine PC

sample shows that it has a somewhat amorphous structure. A broad peak was observed at

2θ=17.63º which corresponds to d-spacing of 5.038 Å. With the addition of 1 and 3 wt.% PEG to

PC, the corresponding d-spacings decreased to 4.582 and 3.619 Å, respectively. For the

13
membrane containing 5 wt.% PEG, d-spacing was increased to 4.065 which is a little higher than

that for the sample containing 3 wt.% PEG. Also, in this composition, a new peak was observed

at 2θ=5.91º corresponding to d-spacing of 14.939 Å. The d-spacings of the membrane containing

5 wt.% PEG, show micro phase separations so that two d-spacings were observed, one for the

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PC/PEG and the other for the separated PEG. It is obvious that the existence of some minor

micro phase separation is responsible for increasing the d-spacing of the sample to 4.065 Å.

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The results clearly reveal that the addition of PEG to PC membranes have resulted in blend

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compositions with lower d-spacings with respect to the pristine PC which could result in better

membranes with higher CO2/CH4 selectivities but lower permeabilities. Considering the kinetic
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diameter for CO2 and CH4 molecules (3.30 and 3.82 Å, respectively), it is predicted that the

membranes containing PEG would result in better CO2/CH4 selectivities in comparison to the
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pristine PC membrane.
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3.2. Permeability and selectivity

The permeability experiments were performed using pure gases. All of the experiments were
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done at room temperature (25±2 °C) and different upstream pressures of 1, 3, 5 and 7 bar. Table
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3 shows the results of the permeation experiments and corresponding selectivities at 3 bar for PC

and PC/PEG blend membranes. The results showed a decrease in the permeabilities both for CO2
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and CH4 with an increase in PEG-300 content into the PC matrix. The permeability of CO2

decreased from 5.66±0.28 barrer for the pristine PC membrane to 4.46±0.49 barrer for the

membrane containing 5 wt.% PEG-300 (about 21%).The results for CO2 permeability are in

agreement with the previously reported results [19, 20, 22, 24, 48, 49]. This can be attributed to

14
the increase in polymer chain packaging by the addition of low molecular weight PEGs. The

molecular structure of the polymer has a great impact on the transport mechanism in the

nonporous membranes. In contrast to the rubbery polymers, the polymer chains in the glassy

polymers such as polycarbonate are restricted and the segments cannot rotate freely around the

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main chain [38, 50, 51]. The addition of soft PEG molecules into the hard PC structure leads to

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an increase in the flexibility of the PC polymer chains in the blend membranes. In this regard, the

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density of the membranes were measured and the corresponding fractional free volume for each

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membrane sample was calculated. The results which are shown in Table 4 revealed that by

addition of the PEG of the pristine PC, the corresponding FFV of the polymer decreased. Then it
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could be concluded that the free volume of the PC have occupied by the small PEG molecules

and hence, the total free volume for permeation have decreased. This decrease in FFV by
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addition of PEG, is responsible for decreasing the permeability and increase in selectivity of the

membranes. By an increase in PEG content of the membranes, the corresponding selectivities

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were increased from 26.6±1.7 for the pristine PC membrane to 36.2±3.4 for the PC/PEG 5 wt.%

membrane at 3 bar which shows more than 36% increase. The high selectivity of the blend
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membranes can be attributed to the interaction between the polar PEG with CO2 molecules, and
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also the presence of the flexible PEG short chains at the amorphous domains of the PC along

with decrease in FFV [34, 35, 37].

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It must be notified that increasing the PEG content over 5 wt.% showed an obvious phase

separation. The membranes containing 7 and 10 wt.% PEG were also fabricated but they were

not transparent and some PEG fine droplets were formed on the surface of the membranes. The

SEM images, DSC thermograms, FTIR spectrums and XRD analysis all show limited miscibility

15
of PEG with PC. It seems that by increasing the PEG content over 1 wt.%, micro phase

separation starts to occur. By increasing the PEG content over 5 wt.% the structure of the

membrane become porous and the selectivity decreased considerably. These observations are in

agreement with the previously reported results for Matrimid/PEG-200 blends [41].

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3.3. Effect of pressure on the permeability and selectivity

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The effect of pressure on permeability and selectivity of the membranes was presented in Fig.

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5(A-C), respectively. According to Fig. 5A, the CO2 permeabilities decreased as the pressure

increased. The lowest permeabilities all over the pressure ranges were observed for the PC/PEG
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5 wt.% membrane. This is due to the greater membrane compaction at higher pressures in the

presence of liquid and low molecular weight PEGs along with the reduction in FFV of the
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membranes by addition of PEG [40]. Similar behavior was observed for the effect of pressure on

methane permeation (Fig. 5B). In Fig. 5C, the effect of pressure on CO2/CH4 selectivity, in the
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range of 1 to 7 bar, is shown. A maximum CO2/CH4 selectivity of 40.9±2.14 is obtained for the

PC/PEG 5 wt. % membrane at 1 bar. According to the selectivity results, the increase in pressure
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leads to a decrease in CO2/CH4 selectivities due to the higher impact of pressure on permeability
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of CH4 than CO2 through the membrane. This could be explained by considering the effect of

pressure on the diffusivity and solubility selectivities considering the d-spacings of the
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membrane structures. In this regard, the effect of pressure on the permeation time lag, diffusion

and solubility coefficients for CO2 as a function of pressure were determined and presented in

Fig. 6(A-C).

16
Fig. 6A shows the pressure dependency of time lag for the permeation of carbon dioxide in PC

and PC/PEG blends. The figure shows that as the pressure is increased, the time lag becomes

shorter which indicates the increase of the diffusion coefficient with pressure. Also, with an

increase in PEG content, the time lag becomes shorter, especially by the addition of 1 wt.% PEG,

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and a considerable decrease in time lag was observed.

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The diffusion coefficient (D) shows how fast the penetrant molecules pass through the

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membrane. It is a function of the penetrant molecule’s size and shape and also the membrane

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structure [52]. Fig. 6B shows the diffusion coefficient of carbon dioxide in PC and PC/PEG

blends as a function of pressure. Almost a linear dependency between the diffusion coefficient
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and pressure was found. The addition of PEG enhanced the diffusion coefficient considerably,

for example, the diffusion coefficient for carbon dioxide at 7 bar increases from 0.62×10-8 m2/s
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for the pristine PC to 4.24×10-8 m2/s for the PC/PEG (5 wt.%) membrane which shows more

than 6.7 times increase. It is clear that the increase of PEG concentration in the PC polymer
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causes an increase in the chain flexibility and consequently increases the diffusion coefficient

[35].
pt

This can also be attributed to reduction in FFV of the membranes by the addition of PEG and
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pressure. With an increase in PEG content and operating pressure, due to the antiplasticization

effect of PEG on PC, the FFV of the membranes decreases and compaction of the membrane by
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applied pressure makes the membranes less penetrative. The effect of pressure on the diffusion

coefficient of CH4 in the membranes is more considerable than that for CO2. This is initially due

to the smaller kinetic diameter of the CO2 molecule (3.30 Å) than that for the CH4 molecule

(3.82 Å) which means that CO2 can diffuse more effectively through the small spacings (d-

17
spacings) even at lower pressures. Secondly, the plasticization effect of CO2 is much higher than

CH4 that means CO2 can plasticize the PC and its blend membranes even at lower pressures [35].

As the PEG content is increased, the changes in diffusion coefficients become smaller and also

less pressure dependency of the diffusion coefficient are observed.

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Fig. 6C shows the effect of pressure and PEG content on the solubility coefficient (S) of CO2 on

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the PC and PC/PEG blend membranes. As the pressure and PEG content is increased, the

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solubility coefficient becomes smaller. A decrease in the solubility coefficient with an increase in

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pressure is related to the dual-sorption mechanism of the sorption of gases into glassy polymers.

As the PEG content is increased, the solubility of CO2 decreases because of reduction in the
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FFV. According to the dual-sorption mechanism in the glassy polymers, the solubility coefficient

is determined by summation of the terms of Henry’s law of solubility (dissolution in continuous

M
chain matrix) and the Langmuir-type of sorption (sorption in micro-voids) [53].

By increasing the pressure and PEG content, the free volume of the polymer is reduced and the
ed

polymer becomes more compact, and then the solubility is decreased [34, 38].

Similar behavior for CH4 sorption and diffusion in the PC and PC/PEG blends was observed.
pt

Figure 7 (A and B) shows the effect of pressure and PEG content on the diffusivity and solubility
ce

coefficient of CH4 in the prepared membranes. Similar trends but with different values are

observed. The solubilities of methane is higher but the diffusivities are lower than carbon dioxide
Ac

in the similar membranes which is related to higher molecular size of methane in comparison

with carbon dioxide [54]. The obtained results for pure PC is in agreement with the previously

reported results in open literature [19, 20, 22, 24, 48, 49].

18
 D  S 
The diffusivity selectivity  CO 2  and solubility selectivity  CO 2  were calculated from the
 DCH 4   SCH 4 

obtained experimental permeation results through the time-lag method at different pressures and

( Di ) p ( Si ) p
PEG contents. Also, the ratio of 1
and 1
for CO2 and CH4 were calculated. By
( Di ) p ( Si ) p

t
ip
2 2

(D )
CO2 1 (D )
CH 4 1

cr
considering P1=1 bar and P2=7 bar, for the pristine PC membrane = 2 and = 19
(D )
CO2 7
(D )
CH 4 7

us
while for PC/PEG (5 wt.%) membranes these values are 2.17 and 2.94, respectively. Therefore,

 DCO2 
 
an  DCH 4 1
the ratio of diffusivity selectivities at P1=1 to that for P2=7 or would be 0.105 and
 DCO2 
 DCH 4 
 7
M

0.740 for the pristine PC and PC/PEG (5 wt.%) membranes, respectively. This means that, by

increasing the pressure from 1 to 7 bar, the diffusion coefficient increase of CH4 with respect to
ed

CO2 is nearly 9.5 times for the pristine PC and 1.35 times for PC/PEG (5 wt.%) membranes.

Similar calculations were done for solubility selectivities and it was found that by increasing the
pt

pressure from 1 to 7 bar, the solubility coefficient decrease of CH4 with respect to CO2 is nearly
ce

0.121 times for the pristine PC and 1.20 times for PC/PEG (5 wt.%) membranes. Then, the ratio

of the diffusivity selectivities to solubility selectivities at the mentioned pressures were

Ac

calculated as 0.87, 0.73, 0.67 and 0.61 for the membrane samples of PC, PC/PEG (1 wt.%),

PC/PEG (3 wt.%) and PC/PEG (5 wt.%), respectively. These results show that by increasing the

pressure, the selectivity decreases and this decrease depends directly on the PEG content.

Moreover, the contribution of diffusivity selectivity is more than solubility selectivity. In other

19
words, with an increase of pressure, the diffusivity selectivity decreases more than solubility

selectivity which is due to the higher increase of methane diffusion coefficient upon the pressure

increase rather than methane.

Diffusivity coefficient of a penetrant in a polymer depends on d-spacing and FFV of the

t
polymer, chemical nature of the penetrant and the interaction between the penetrant and the

ip
polymer. It is well known that an increase of feed pressure has a compression effect on the

cr
membranes so that as the pressure is increased, the membrane becomes denser and free volume

us
decreases. On the other hand, both CO2 and CH4 are condensable gases which plasticize the

polymeric membranes. Considering the obtained d-spaces from XRD analysis (Table 2), it is
an
clear that the d-spaces are large enough for easy diffusion of small CO2 molecules but they are

marginal for diffusion of CH4 larger molecules. It has been shown that immersion of the PC
M
membrane to the plasticizing gases would plasticize the membrane and increase the d-spacing.

On the other hand, the selectivity increases as the PEG content is increased. This could be related
ed

to the molecular nature of carbon dioxide and its interaction with PEG. Although CO2 is a

nonpolar molecule, in its polar C=O bonds the oxygen atom has a higher electron affinity than
pt

the carbon atom and then the electron cloud is pulled towards the oxygen atom. Thus, it can
ce

interact with polar groups of PEG molecules and consequently causes an increase in selectivity

[35, 37].
Ac

20
4. Comparison with other membranes

Table 5 shows a comparison between the separation performances of the prepared PC and

PC/PEG membranes in the current study and the reported results for PC dense membranes in

t
ip
open literatures, all for CO2/CH4 systems. All of the reported data have been measured at

temperature of 35 ºC and the pressures varied from 1 to 10 bar. It could be observed that the

cr
reported permeabilities for CO2 are in the range of 6.0 to 8.5 barrer and for CH4 in the range of

us
0.26 to 0.36 barrer which have resulted selectivities from 18.9 to 26.6. Most of the reported

results are belong to the bisphenol-A polycarbonate under trade name of Lexan which had a
an
molecular weight of 46000 g/mol. The results obtained in the current study for the pristine PC

and PC/PEG (5 wt. %) are shown in the last two rows of the Table 5. Generally, the
M

permeabilities of the PC membrane for both CO2 and CH4 are higher than the reported results by

other researcher that is attributed to lower molecular weight of the PC which was used in the
ed

current study respect to Lexan (23000 and 46000 g/mol, respectively). The obtained selectivity

for the pristine PC membrane is completely in agreement with the previously reported results at
pt

1 bar [23, 56]. Addition of 5 wt.% PEG-300 to the PC have decreased both CO2 and CH4
ce

permeabilities but the effect of PEG addition on CH4 permeability reduction is more than that for

CO2 so that the selectivity has increased from 26.6±0.99 to 40.9±2.14 (53% increase) which
Ac

could be considered as a good achievement. These permeability and selectivity are in the range

of the reported results for highly expensive polymeric membrane materials such as polyimides

like Matrimid 5218 [41].

21
5. Conclusions

PC/PEG blend membranes were fabricated by blending 0-5 wt.% polyethylene glycol (PEG-300)

with polycarbonate (PC) for CO2/CH4 separation. The fabricated membranes were characterized

t
ip
using DSC and SEM. The DSC results showed that by increasing the PEG content in the blend

membranes, a shift to the lower values occur in the glass transition temperature of the blends. In

cr
addition, the SEM images confirmed a homogenous pattern without macro-voids or defects both

us
at the surface and cross-sections of the PC and PC/PEG blend membranes. The gas permeation

results showed that the CO2/CH4 selectivity increases with increasing the PEG content of the
an
blend membranes but it decreases by increasing the feed pressure. The permeability of the

membranes decreased both by an increase in feed pressure and PEG content. It is believed that
M

the PC/PEG blend membranes could be proposed as effective candidates for methane separation

from raw biogas in biogas treatment plants.

ed

6. Acknowledgements
pt

This work was partially supported by Young Researchers Club of Islamic Azad University
ce

(Omidiyeh Branch) which is acknowledged. Special thanks to H. Sanaeepur and S.A. Alavi and
Ac

A. Ebadi Amooghin for their helpful assistances and inspections.

22
7. Symbols

A Mmembrane effective area (cm2)

D diffusivity coefficients (cm2/s)

t
ip
FFV Fractional free volume, (-)

l membrane thickness (cm)

cr
P gas permeability (Barrer)

us
PC polycarbonate

PEG polyethylene glycol

an
S solubility coefficients (cm3 (STP)/cm3cmHg)

Tg glass transition temperature (°C)

M

V0 volume occupied by the polymer chains, (cm3/mol)

Vsp specific volume of polymer, (cm3/mol)

ed

Vw Van der Waals volume of the polymer chain, (cm3/mol)

α ideal separation factor (-)

pt

θ time-lag (s)
ce

ρ density (g/cm3)
Ac

23
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ip
Vaughn, J.T., Koros, W.J., 2014. Analysis of feed stream acid gas concentration effects on the

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cr
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us
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ip
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ed
pt
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31
Table 1– The thermodynamic properties of CO2 and CH4 [1].

Size Condensability

Critical volume Kinetic diameter Normal boiling Critical

t
ip
(cm3/mol) (Å) point (K) temperature (K)

cr
CO2 94.07 3.30 194.7 304.12

us
CH4 98.6 3.82 111.66 190.56
an
M
ed
pt
ce
Ac

32
Table 2- XRD analysis results for the position of the peak maxima and d-spacings for the
fabricated membranes.

Membrane Pos. [°2θ] d-spacing [Å]

PC 17.63 5.038

t
PC/PEG (99:1) 19.36 4.582

ip
PC/PEG (97:3) 24.59 3.619

cr
PC/PEG (95:5) 21.86 4.065

us
PC/PEG (95:5) 5.91 14.939
an
M
ed
pt
ce
Ac

33
Table 3- The permeability and selectivity of PC and the PC/PEG blend membranes at 3 bar and
25±2 °C.

PEG content PCO2

PCH4 (Barrer) αCO2/CH4
(wt.%) (Barrer)

t
ip
0 5.66±0.28 0.21±0.01 26.6±1.7

1 5.43±0.38 0.20±0.02 27.7±2.1

cr
3 5.36±0.48 0.17±0.01 32.1±2.7

us
5 4.46±0.49 0.12±0.01 36.2±3.4
an
M
ed
pt
ce
Ac

34
Table 4- The effect of PEG concentration on the FFV of the modified membranes.

Mw ρ VW V0 Vsp FFV FFV change

Membrane
(g/mol) (g/cm3) (cm3/mol) (cm3/mol) (cm3/mol) (%)

PC 254.3 1.140 144.3 0.738 0.877 0.159 -

t
PC/PEG 254.7 1.167 143.2 0.731 0.857 0.147 -7.83

ip
(99:1)

cr
PC/PEG 255.5 1.193 141.2 0.718 0.838 0.143 -10.18

us
(97:3)

PC/PEG 256.3 1.223 139.1 0.706 0.818 0.137 -13.89

an
(95:5)

PEG 300 300.00 1.125 22.53 0.098 0.889 0.890 -

M
ed
pt
ce
Ac

35
 Table 5 – Comparison of the obtained results in this study with the reported results in open
literature.

Membrane T (°C) p (atm) PCO2 (barrer) PCH4 (barrer) α (CO2/CH4) Ref.

Lexan PC 35 1 8.5 0.32 26.5 [23]

t
PC 35 1 6.0 0.26 23.3 [25]

ip
Lexan PC 35 1 7.1 0.29 24.4 [48]

cr
Lexan 8800-112 PC 35 10 6.8 0.36 19.0 [55]

us
Lexan 131-111 PC 35 1 8.0 0.30 26.6 [56]

Lexan PC 35 5 8.0 0.34 23.5 [57]

an
Lexan PC 35 1 6.8 0.36 18.9 [58]

PC 25±2 1 9.4±0.32 0.35±0.01 26.6±0.99 This work

M
PC/PEG-300 (95:5) 25±2 1 6.69±0.43 0.16±0.01 40.9±2.14 This work
ed
pt
ce
Ac

36
Figure 1- FTIR spectrums for the studied membranes.

t
ip
cr
us
an
M
ed
pt
ce
Ac

37
Fig. 2. SEM images of the cross section and top surface of the membranes (a, b) PC; (c, d)
PC/PEG (1 wt. %); (e, f) PC/PEG (3 wt. %); (g, h) PC/PEG (5 wt.%).

t
ip
cr
us
an
M
ed
pt
ce
Ac

38
Fig. 3. DSC thermograms of the pristine PC and PC/PEG blend membranes.

t
ip
cr
us
an
M
ed
pt
ce
Ac

39
Fig. 4. XRD patterns for the pristine PC and PC/PEG blend membranes.

t
ip
cr
us
an
M
ed
pt
ce
Ac

40
Fig. 5. The effect of pressure on the (A) CO2 permeability (B) CH4 permeability and (C)
CO2/CH4 selectivity of PC and the PC/PEG blend membranes at 25±2 °C.

t
ip
cr
us
an
M
ed
pt
ce
Ac

41
Fig. 6- Pressure dependency of (A) time lag, (B) diffusion coefficient, and (C) solubility
coefficient for CO2 in PC and PC/PEG blend membranes at 25±2 °C.

t
ip
cr
us
an
M
ed
pt
ce
Ac

42
Fig. 7. Pressure dependency of (A) diffusion coefficient and (B) solubility coefficient for CH4 in
PC and PC/PEG blend membranes at 25±2 °C.

t
ip
cr
us
an
M
ed
pt
ce
Ac

43