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Gas Solubility, Diffusivity and Permeability in Poly (Ethylene Oxide)
Gas Solubility, Diffusivity and Permeability in Poly (Ethylene Oxide)
Received 14 March 2003; received in revised form 7 August 2003; accepted 25 August 2003
Abstract
The effect of pressure on the solubility, diffusivity, and permeability of He, H2 , O2 , N2 , CO2 , CH4 , C2 H4 , C2 H6 , C3 H6 and C3 H8 in
poly(ethylene oxide) (PEO) is reported at 35 ◦ C. Additionally, the temperature dependence of permeability is reported. The effect of polar
ether linkages in PEO on gas transport is illustrated by comparing transport properties in PEO with those in polyethylene (PE). For example,
at 35 ◦ C and infinite dilution, semi-crystalline PEO exhibits CO2 permeability coefficient of 12 Barrers, and CO2 /H2 and CO2 /N2 pure gas
selectivities of 6.7 and 48, respectively. In contrast, at similar conditions, the permeability of PE to CO2 is 13 Barrers, but the CO2 /N2 selectivity
is only 13. In addition to good separation properties for quadrupolar–nonpolar gas pairs, PEO also shows interestingly high selectivity for
olefins over paraffins, which is ascribed to favorable interaction between the polar ether groups in PEO and olefins. For example, the infinite
dilution permeability of PEO to propylene is 3.8 Barrers and pure gas propylene–propane selectivity is 2.7 at 35 ◦ C. At similar conditions, PE
exhibits propylene–propane selectivity of only 1.4.
© 2004 Elsevier B.V. All rights reserved.
0376-7388/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2003.08.031
106 H. Lin, B.D. Freeman / Journal of Membrane Science 239 (2004) 105–117
Table 1 2. Background
Gas transport properties in block copolymers containing similar amounts
of poly(ethylene oxide) segments and a variety of hard segments
The permeability of a polymer to a gas A, PA , is [4]:
Hard segmenta PEO (wt.%) PCO2 [Barrer] PCO2 /PN2
NA l
PA ≡ (1)
Polyimide p2 − p 1
PMDA-pDDS [10] 68.6 238 49
BPDA-ODA [10] 62.3 117 51 where NA is the steady-state flux of gas through the film, l
Polyamide is the film thickness, and p2 and p1 are the upstream (i.e.,
IPA-ODA [10] 68.3 58 53 high) and downstream (i.e., low) partial pressures of gas
PA12 [17] 55 120 51 A, respectively. If the diffusion process obeys Fick’s law,
PA6 [17] 57 66 56 and the downstream pressure is much less than upstream
Polyurethane pressure, the permeability is given by [4]:
MDI-BPA [10] 60.5 48 47
a
PA = DA SA (2)
The detailed chemical structures are available in the corresponding
references. The gas permeability was measured at 35 ◦ C and 200 kPa where DA is the average effective diffusivity through the
(2 atm) in [10], and at 35 ◦ C and 1.0 MPa (10 atm) in [17].
film, and SA is the apparent sorption coefficient [4]:
C2
SA = (3)
gas selectivity is similar among all these materials, gas p2
permeability varies significantly. These results suggest that where C2 is the concentration of gas dissolved in the polymer
the PEO phase is the continuous path for gas permeation when the gas pressure in contact with the polymer is p2 .
[10,17], and gas permeability depends strongly on the de- The ideal selectivity of a membrane for gas A over gas B
tailed morphology, such as domain shape and interspatial is the ratio of their pure gas permeabilities [4]:
arrangement, which could be influenced by the hard seg-
PA DA SA
ment composition and the length of PEO and hard segment αA/B = = (4)
blocks. PB DB SB
Despite this interest in PEO-based materials for acid gas where DA /DB is the diffusivity selectivity, the ratio of the
selective separations, a systematic study of the solubility, dif- diffusion coefficients of gases A and B. The ratio of the solu-
fusivity, and permeability properties of pure poly(ethylene bilities of gases A and B, SA /SB , is the solubility selectivity.
oxide) has not been reported, due in large measure to its high Diffusivity selectivity is strongly influenced by the size dif-
crystallinity and, consequently, low transport property val- ference between the penetrant molecules and the size-sieving
ues. In this study we present physical characterization and ability of the polymer matrix, whereas solubility selectivity
gas transport properties of solution cast PEO films. The ef- is controlled by the relative condensability of the penetrants
fect of pressure on gas permeability, diffusivity and solubil- and the relative affinity between the penetrants and the poly-
ity is reported for a variety of nonpolar gases (He, H2 , O2 , mer matrix [4].
N2 ), a series of olefinic and aliphatic hydrocarbons (CH4 , Gas transport properties in a semi-crystalline polymer
C2 H6 , C2 H4 , C3 H8 , C3 H6 ), and CO2 . The effect of tem- such as PEO are usually modeled by assuming that the crys-
perature on permeability is also reported. Relevant physical tals act as an impermeable dispersed phase imbedded in an
properties of these penetrants, which will be used later in amorphous phase and by then developing models for the in-
the discussion, are recorded in Table 2. fluence of crystallinity on solubility and diffusivity. In a rub-
bery polymer, the effect of crystallinity on penetrant sorp-
tion is typically represented as follows [22]:
Table 2
SA = SA,a φa (5)
Penetrant parameters characterizing size (critical volume) and condens-
ability (critical temperature) where SA is the observed solubility coefficient, SA,a is the
Size (critical volume Condensability (critical solubility coefficient in the amorphous polymer, and φa is
[39] (cm3 /mole)) temperature [39] (K)) the amorphous phase volume fraction.
He 57.4 5.19 The influence of crystallinity on diffusivity is traditionally
H2 65.1 33.24 described as follows [23]:
O2 73.4 154.6
N2 89.8 126.2 DA,a
DA = (6)
CO2 93.9 304.21 τβ
CH4 99.2 191.05
C 2 H4 130.4 282.40 where DA,a is the diffusion coefficient in the amorphous
C 2 H6 148.3 305.35 polymer, τ is a tortuosity factor, and β is a chain im-
C 3 H6 181.0 364.9
mobilization factor. τ characterizes the tortuosity of the
C 3 H8 203.0 369.8
amorphous phase caused by the presence of impermeable
H. Lin, B.D. Freeman / Journal of Membrane Science 239 (2004) 105–117 107
crystallites dispersed in it. Simple models from compos- PEO is susceptible to oxidative degradation, due to the pres-
ites theory, such as the one given below, are often used to ence of weak C–O bonds in the backbone [24], the anneal-
describe the influence of crystallinity on tortuosity [23]: ing time needed to be as short as possible and the annealing
1 temperature needed to be as low as possible. Therefore, to
τ= (7) minimize the degradation and prepare a nonporous film, we
φa
decided to anneal the sample under vacuum just above its
The chain immobilization factor, β, accounts for the re- melting temperature for 2 h.
stricted segmental mobility in the amorphous phase by
crystallites. In the simplest case, when β = 1 (i.e., no chain 3.2. Density
immobilization), gas permeability is given by [23]:
PA = SA DA = PA,a φa2 (8) Polymer film density was determined by hydrostatic
weighing using a Mettler Toledo balance (Model AG204,
where PA,a is the estimated permeability of penetrant A in Switzerland) and a density determination kit [25]. In this
amorphous phase polymer. method, a liquid with a known density (ρo ) (the so-called
Generally, crystallites decrease both gas diffusivity and auxiliary liquid) is needed, and the film density (ρ) is
solubility. By reducing amorphous phase polymer chain mo- calculated as follows:
bility, crystallites can also increase activation energy of dif- MA
fusion, especially for larger penetrants [23]. These effects ρ= ρo (9)
MA − M L
become more pronounced as the crystalline volume fraction
increases or as crystallite size decreases [23]. where MA is the film weight in air, and ML is the film
weight in the auxiliary liquid. Iso-octane was used as the
auxiliary liquid because PEO is reported to be insoluble in
3. Experimental iso-octane [26]. The film weight determination in iso-octane
was performed as quickly as possible to reduce any swelling
3.1. Materials and sample preparation of PEO due to iso-octane sorption.
3.5. Sorption measurements where H is the melting enthalpy, obtained from the area
under the melting endotherm, and Hc is the melting en-
Gas solubility was determined using a dual-volume, dual- thalpy of 100% crystalline PEO. From the DSC experiment,
transducer apparatus based on the barometric, pressure- H was 121 J/g, which is close to the literature value of
decay method [16]. Polymer samples were degassed by 125 J/g for PEO with a molecular weight of 4,000,000 [27].
exposure to vacuum in the sorption cell overnight before A variety of values of Hc exist in the literature ranging
beginning sorption measurements and between each gas. from 166.4 to 265 J/g [26]. In this study, we used the value
Because PEO is highly crystalline and, therefore, exhibits of 166.4 J/g suggested by Simon and Rutherford [30]. Us-
low solubility, the uncertainty in the measured solubility co- ing this value in Eq. (11) yields a crystallinity value of
efficients of the low sorbing permanent gases was high. For 72.7 wt.%.
example, the uncertainty in solubility was estimated to be Volume fraction crystallinity, φc , was calculated as fol-
±50% for N2 , O2 and CH4 , and less than 10% for the other lows:
penetrants. Solubilities of H2 and He at 35 ◦ C were too low
ρ
to measure. Uncertainty was estimated by a standard propa- φc = χc (12)
ρc
gation of errors analysis [29], where uncertainties of all rel-
evant measured parameters propagate and contribute to the where ρ is the measured PEO density and ρc is the crystal
uncertainty of the solubility. The dominant contribution to density calculated from the unit cell dimensions of a PEO
the uncertainty comes from the uncertainty in measuring the crystallite, which is 1.234 g/cm3 at room temperature [30].
pressure in the sorption cell. For this measurement, we use PEO film density, ρ, was 1.209 g/cm3 , which is consistent
the two Sensotec pressure transducers (Model Super THE), with values (1.20–1.22 g/cm3 ) reported in the literature for
and the uncertainty in the measured pressure is ±1.7 kPa PEO [25]. Using Eq. (12), the crystallinity was 71 vol.%.
(±0.017 atm). The full pressure range of the transducer is The volume percent crystallinity can also be estimated
0–3.4 MPa (0–34 atm). from the density using the following relation:
ρ − ρa
φc = (13)
ρc − ρ a
4. Results and discussion
where ρa is the density of amorphous PEO (1.124 g/cm3 )
4.1. Thermal and physical characterization [30]. The φc value calculated from Eq. (13) was 0.77, which
is consistent with that obtained from Eq. (12). In the remain-
Fig. 1 presents a first scan DSC thermogram of PEO. The der of this report, the crystallinity calculated from the DSC
peak of the melting endotherm is 68 ◦ C, which is near the result will be used to estimate amorphous phase permeabil-
value of 66 ◦ C reported for PEO with a molecular weight of ity and solubility values.
1,000,000 [30]. The weight fraction crystallinity in the film, Transport properties in polymers are sensitive to the
χc , was estimated as follows [27]: amount of free volume in the polymer matrix [4]. In semi-
crystalline polymers such as PE and PEO, transport is
H presumed to occur only in the amorphous regions of the
χc = (11)
Hc polymers, so it is of interest to compute the fractional free
H. Lin, B.D. Freeman / Journal of Membrane Science 239 (2004) 105–117 109
Table 3
Physical property comparison between poly(ethylene oxide) and
poly(ethylene)
Polymer Tg a (◦ C) FFVb Densityc Crystallinity Solubility
(g/cm3 ) (vol.%) parameter
(MPa1/2 )
[26]
PEO −50 0.139 1.124 71 19.8
PE −44 0.188 0.854 43d 16.6
a In these polymers, Tg depends strongly on the degree of crystallinity
[50]. The value reported for PEO corresponds to 74 vol.% crystallinity
[50]. The value reported for PE corresponds to a sample with 43 vol.%
crystallinity; in a PE sample having 71 vol.% crystallinity, the Tg would be
−10 ◦ C [50]. If one extrapolates to hypothetical wholly amorphous PEO
and PE, the estimated Tg values are −85 and −80 ◦ C, respectively [50].
b FFV values based on estimated density of amorphous PE and PEO.
c Estimated density of wholly amorphous polymer at room temperature.
d Alathon 14 polyethylene was chosen from the reference by Michaels
and Bixler [22]. Later in this report, gas transport properties of Alathon
14 are compared with those of PEO.
Fig. 2a and b present permeability coefficients for gases simple empirical model [33]:
at 35 ◦ C as a function of upstream pressure. For the perma- PA = PA,o (1 + m p) = PA,o (1 + mp2 ) (15)
nent gases (He, H2 , O2 , and N2 ), permeability coefficients
are essentially independent of pressure, while the permeabil- where PA,o is the permeability coefficient at an upstream
ity coefficients of CO2 and hydrocarbons such as C3 H8 in- pressure, p2 , of 0 (i.e., infinite dilution permeability), m the
crease with increasing pressure. This behavior is consistent adjustable constant, and p is the difference between the
with gas permeation properties in rubbery polymers [33]. upstream and downstream pressure, p = p2 − p1 . Since
For strongly sorbing penetrants, such as CO2 and C3 H8 , high downstream pressure, p1 is much less than upstream pres-
penetrant concentrations can plasticize the polymer matrix sure p2 , p can be replaced by p2 . Infinite dilution perme-
by increasing polymer local segmental motion, thus enhanc- ability coefficients for different penetrants were calculated
ing penetrant diffusion coefficients and, in turn, permeabil- using Eq. (15). Estimated amorphous phase permeability
ity [34]. Additionally, the solubility of condensable compo- coefficients were estimated using Eq. (8). This calculation
nents typically increases with increasing pressure, and this presumes that tortuosity obeys Eq. (7) and that the chain
factor also acts to increase permeability coefficients [35]. immobilization factor, β, is unity. Because we did not have
For the data in Fig. 2a,b, the pressure dependence of the PEO samples with varying levels of crystallinity, neither of
permeability coefficients may be described by the following these assumptions can be tested. As a result, the estimated
110 H. Lin, B.D. Freeman / Journal of Membrane Science 239 (2004) 105–117
Table 4
Penetrant permeation parameters in semi-crystalline and amorphous poly(ethylene oxide) and in amorphous polyethylene [22,23]
Gas PEO PE
a
PA,o (Barrer) m× 103 (atm−1 ) b
PA,a (Barrer) Ep (kJ/mole) PA,o (Barrer) PA,a b (Barrer)
amorphous phase permeability coefficients should be re- CO2 permeability in amorphous phase PEO is within the
garded as rather crude estimates of the actual permeation range of values reported for block copolymers containing
properties of the amorphous material. These data are re- PEO (cf. Table 1). The CO2 /H2 pure gas selectivity in PEO
ported in Table 4. The permeability coefficients decrease in is 6.7 at infinite dilution and increases to 9.9 at 1.5 MPa
the following order: (14.7 atm), which is similar to values reported for polyether-
b-polyamide segmented block copolymers [17]. To empha-
CO2 > C3 H6 > C2 H4 > H2 ≈ He > C3 H8 size the effect that this difference in properties for CO2 has
≈ C2 H6 > CH4 ≈ O2 > N2 on separation, one can also consider the CO2 /N2 selectivity.
In PE, the pure gas CO2 /N2 selectivity at infinite dilution is
Except for CO2 and the olefins, this order of permeability approximately 12. However, in polar PEO, the CO2 /N2 pure
coefficients is typical for rubbery polymers [33]. Generally, gas selectivity at infinite dilution is 48, which is essentially
penetrants with higher critical temperature are more con- equivalent to the selectivity in block copolymers containing
densable and, therefore, more soluble; however, more con- PEO, as shown in Table 1. These results are consistent with
densable penetrants often have larger critical volume values enhanced solubility of quadrupolar CO2 in PEO.
(cf. Table 2), which reduces diffusion coefficients. Perme- It is also of interest to explore the difference between
ability reflects the tradeoff between these often conflicting olefin and paraffin transport in these two polymers because
contributions from solubility and diffusivity. of the importance of this separation to the petrochemical
The gas transport properties of polyethylene (PE) have industry [36]. In amorphous PE, propane and propylene have
been well studied [22,23]. Polyethylene provides an inter- very similar permeability coefficients, and the C3 H6 /C3 H8
esting material for comparison with PEO because PE is selectivity is only 1.4 (cf. Table 5). However, in amorphous
essentially PEO without the polar ether linkages. Several PEO, olefins exhibit significantly higher permeability than
physical properties of these two polymers are compared in their paraffin analogues. The pure gas C3 H6 /C3 H8 selectivity
Table 3. The amorphous phase FFV of PEO is significantly at infinite dilution and 35 ◦ C is 2.7, which is almost 100%
lower than that of PE, and the solubility parameter of PEO
is higher than that of PE. These trends are qualitatively
consistent with the much more polar nature of PEO. Table 5
Table 4 presents a comparison of infinite dilution perme- Estimated amorphous phase propylene permeability, diffusivity and sol-
ubility, and C3 H6 /C3 H8 selectivity in PE at 25 ◦ C and PEO at 35 ◦ C at
ability coefficients in amorphous PEO and PE. Unlike PEO, infinite dilution
literature values for tortuosity and chain immobilization fac-
Propylene sorption and Propylene–propane
tors are available for PE [23], and these data were used to transport properties selectivity
estimate amorphous phase permeability coefficients in PE.
PEb PEO PE PEO
With the exception of CO2 , PE exhibits higher permeability
values than PEO, even though the PE data were determined PA a 147 45 P= /P c 1.4 2.7
Da a × 107 D= /D c
at lower temperature (25 ◦ C, rather than 35 ◦ C for PEO). 3.2 1.7 1.5 1.6
SA a 3.5 2.0 S= /S c 0.89 1.7
CO2 is the only gas exhibiting higher permeability in PEO
a The units for permeability (P), diffusivity (D) and solubility (S) are
than in PE. Interestingly, CO2 is much more permeable than
Barrer, cm2 /s, and cm3 (STP)/(cm3 polymer atm), respectively.
all of the other gases considered, including H2 , which, in b Michaels and Bixler [22,23].
conventional glassy gas separation polymers, always has a c The subscripts “ ‘’ and “ ” represent propylene and propane, respec-
=
higher permeability coefficient than CO2 [4]. The estimated tively.
H. Lin, B.D. Freeman / Journal of Membrane Science 239 (2004) 105–117 111
Table 7
Pure gas selectivity in semi-crystalline poly(ethylene oxide) as a function
of pressure and temperature
Pressure (atm) Pure gas selectivity
25 ◦ C 35 ◦ C 45 ◦ C
O2 /N2
4.4 2.8 2.5
7.8 3.7 2.8 2.6
14.6 3.1 2.5
CO2 /N2
4.4 55 40
7.8 140 63 48
14.6 79 52
CO2 /CH4
4.4 21 10
7.8 51 23 12
14.6 50 25 13
CO2 /H2
4.4 7.4 6.2
7.8 9.5 8.4 6.9
14.6 12 9.9 7.7
C2 H4 /C2 H6
4.4 2.3 1.8 1.6
7.8 2.4 1.7 1.6
11.2 1.9 1.7 1.7
C3 H6 /C3 H8
4.4 3.9 3.0 2.6
7.8 4.4 3.1 2.7
Table 9
Diffusion coefficient comparison in semi-crystalline (DA ) and amorphous
(DA,a ) poly(ethylene oxide) at 35 ◦ C and poly(ethylene) at 25 ◦ C
Gas PEO PE
4.4. Diffusivity
5. Conclusion
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