Chemical Engineering Science 62 (2007) 36543659

www.elsevier.com/locate/ces
Diffusion anomaly and blind pore character in carbon molecular
sieve membrane
Kean Wang

School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459, Singapore
Received 23 December 2006; received in revised form 18 March 2007; accepted 22 March 2007
Available online 30 March 2007
Abstract
The structure of a carbon molecular sieve (CMS) membrane is characterized by the through pores and blind pores with non-linear sorption
isotherms inside. Time-lag analysis was conducted for gas permeation in such a structure and mathematical formulations were derived for two
cases. It is found that the pressure dependence of the time lag is dominated by the ratio of sorption afnities in the two types of pores. The
experimental permeation data of pure component CO
2
and N
2
measured on a CMS membrane were used to validate the model. It is found
that, for the adsorbing species (CO
2
), the model is able to well describe the diffusion anomalies over a wide range of permeation pressure,
while for the weakly adsorbing species (N
2
), the model is inadequate to cope with the anomalies at the low end of permeation pressure.
2007 Elsevier Ltd. All rights reserved.
Keywords: Diffusion; Adsorption; CMS; Blind pores; Time lag
1. Introduction
It is a common experimental observation that diffusion of
adsorbed phase in microporous media (carbon molecular sieve
or CMS, in particular) presents stronger functional dependence
on loading than the popular Darken relation (Ash et al., 1963;
Wang et al., 2001, 2007; Rutherford et al., 2003; Ruthven,
2004; Yang, 2003). This diffusion anomaly (also referred to
as non-Fickian diffusion) has been attributed to such effects
as surface heterogeneity (Wang et al., 2001, 2007), multilayer
sorption and interaction of the adsorbed species (Yang, 2003),
local isotherms (Ruthven, 2004), and the existence of blind
pores (a general expression for dead-end pores or ink-bottle
pores) (Ash et al., 1963; Rutherford et al., 2003).
The role of blind pores in transient state mass transfer has
long been noted and investigated with transient uptake in a
batch adsorber or time lag in a permeation rig. For example,
Goodknight and Fatt (1961) investigated the effect of blind
pores in the permeation of non-adsorbing species in porous

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E-mail address: mkwang@ntu.edu.sg.
0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.03.032
media. The blind pores are assumed to be concentration sinks
uniformly distributed along the diffusion path. It was found that
blind pores only affect the early shape of time-lag curve but
will not change the time-lag value.
Ash et al. (1967) investigated the permeation time lags of
sorptive and non-sorptive gases in microporous media and pro-
posed that the time-dependent diffusion coefcient from the
partially blind pores can result in non-Fickian diffusion com-
ponents. Petropoulos et al. recently measured various modes
of permeation time lag (adsorptive/desorptive) for weakly
adsorbing gaseous species (He, Ne, and N
2
) on carbon pel-
lets constructed by multi-step compaction of carbon powders
(Galiatsatou et al., 2006). The experimental results were stud-
ied by the comprehensive time-lag analysis method and they
found that the diffusion coefcient is predominantly spatial
dependent with no signicant contribution from blind pores.
A few recent studies also pointed to the importance of blind
pore character in CMS. Steel and Koros (2005) investigated gas
permeations in four carbon membrane samples fabricated at
various conditions and found that the microporous network can
be characterized by sieving pores and sorption pores. This is
partly agreed by the molecular simulation by Vieira and Seaton
(2003), which suggests that gas permeation (in microporous
K. Wang / Chemical Engineering Science 62 (2007) 36543659 3655
Fig. 1. The schematic structure of a CMS and its idealized model.
carbon membrane) is dominated by the critical path (pore con-
nectivity). Rutherford et al. (2003) measured the transient up-
take of CO
2
and CH
4
on a commercial CMS and found that
the pore mouth resistance of the ink-bottle pores could be the
cause of diffusion anomalies. Lagorsse et al. (2004) measured
the sorption equilibrium, transient uptake, and steady-state per-
meation on CMS membranes and concluded that blind pores
can result in diffusion anomalies and are responsible for the
discrepancy between the diffusion coefcients derived from the
transient state uptake and steady-state permeation.
The purpose of this paper is not to accurately quantify the
volume fraction of blind pores in a CMS membrane, but rather
to demonstrate its role in the transient mass transfer processes
that, for adsorbing species, the diffusion anomalies can be the
result of blind pore characters.
2. Theory
The microporous network of a CMS membrane is charac-
terized by two types of pores, i.e., (1) the through pores (con-
nected pores) and (2) the blind pores. The blind pores are of
the same size and volume and distributed uniformly along the
diffusion path (through pores) (Goodknight and Fatt, 1961).
This ideal structure (Fig. 1) is an oversimplication for a real
CMS. However, it catches the basic features of blind pores and
facilitates the theoretical analysis.
The sorption isotherms in the through and blind pores are
assumed to follow the Langmuir equation, respectively. The
overall isotherm is then the dual-Langmuir equation:
C

=
T
C
T

+(1
T
)C
B

=
T
C
T
s
b
T
P
T
1 +b
T
P
T
+(1
T
)C
B
s
b
B
P
T
1 +b
B
P
T
, (1)
where C

is the adsorbed phase concentration with the capacity

of C
s
, b is the sorption afnity,
T
is the volume fraction of
through pores, P is the hypothetical bulk pressure in microp-
ores, and the subscripts T and B represent the through pore
and blind pore, respectively.
The mass balance for a slab CMS membrane with the thick-
ness of l can be written as

T
jC
T

jt
+(1
T
)
jC
B

jt
=
j
jr
_

T
D(C
T

)
jC
T

jr
_
, (2)
where t is the time, r is the diffusion coordinate, and D

is the
diffusion coefcient which follows the Darken relation,
D

=D
0

_
j ln P
j ln C

_
T
=
D
0

1
T
, (3)
where D
0

is the diffusion coefcient at zero loading and

T
is
the fractional surface loading in through pores. The boundary
conditions for Eq. (1) are
P =P
0
at r =0, (4a)
P =0 at r =l, (4b)
C
T

=0 and C
B

=0 at t =0. (4c)
With the boundary conditions in Eqs. (4), the steady-state hy-
pothetical bulk pressure prole (P

) is
P

=[(1 +b
T
P
0
)
(1x)
1]/b
T
. (5)
And the overall permeation time lag, L, is derived using the
method of Frisch as
L =L
T
+L
B
=
l
2

_
1
0
_
1
x
[C
T

+C
B

] dz dx
_
P
0
0
D

T
(P) dP
=
l
2

_
1
0
_
1
x
C
T

dz dx
_
P
0
0
D

T
(P) dP
+
l
2

_
1
0
_
1
x
C
B

dz dx
_
P
0
0
D

T
(P) dP
, (6)
where x = r/l is the normalized diffusion path and f
T
(P) is
the sorption isotherm in through pores. The overall time lag
is seen to consist of two components: (1) the diffusional time
lag in the through pores (L
T
), and (2) the sorption of diffusing
species in the blind pores (L
B
). The blind pores function as the
concentration sinks along the diffusion path. As the volume
fraction of through pores (
T
) cannot be decided a priori, the
volume fractions of through pores and blind pores are lumped
into the related sorption capacities, respectively.
The analytical solutions for L
T
were same as the expressions
previously derived by Wang et al. (2001) and Strano and Foley
(2002):
L
T
=
l
2
D
0

_
1
ln(1 +b
T
P
0
)
_
1
2

1
(1 +b
T
P
0
) ln
2
(1 +b
T
P
0
)

ln(1 +b
T
P
0
) 1
ln
2
(1 +b
T
P
0
)
__
. (7a)
Eq. (7a) has the power series approximation of
L
T
=
l
2
D
0

_
1
6

bP
0
24
+
7b
2
P
2
0
240

17b
3
P
3
0
720
+
41b
4
P
4
0
2016
+
_
. (7b)
3656 K. Wang / Chemical Engineering Science 62 (2007) 36543659
It is seen that, as P
0
0, L
T
=l
2
/6D
0

, which is the traditional

permeation time lag for non-adsorbing species in a membrane
of slab geometry.
To derive the time lag in blind pores (L
B
), two situations
need to be considered. When k =b
B
/b
T
>1, we have
L
B
=
l
2
D
0

C
B
s
C
T
s
_
2 di log(k/(k 1)) 2 di log(kw/(k 1)) 2 ln(1 k +kw) ln(kw/(k 1)) +k ln
2
w
_
2(k 1) ln
3
w
, (8a)
where w = (1 + b
T
P
0
). The dilogarithm function is dened
as di log(x) =
_
x
0
(ln(t )/(1 t )) dt (with di log(1) = 0 and
di log(0) =
2
/6). The power series approximation of Eq. (8a)
is
L
B
=
l
2
D
0

C
B
s
C
T
s

_
k
6

(2k 1)kb
T
24
P
0
+
(12k
2
2k 3)b
2
T
240
P
2
0
+
_
.
(8b)
Eq. (8b) reduces to the traditional time-lag expression when
P
0
0. When k <1, we have
L
B
=
l
2
D
0

C
B
s
C
T
s
_
2 di log((1 k +kw)/(1 k)) 2 di log(1/(1 k)) 2 ln(1 k) ln w +k ln
2
w
_
2(k 1) ln
3
w
. (9)
The power series expression of Eq. (9) is complicated and
presents no nite limit when P
0
0.
It is seen that the ratio of sorption capacities (in the two type
of pores) mainly affects the magnitude of the time lag, while
the ratio of the sorption afnities (k) plays a critical role in
the pressure dependence of the time lag. The performances of
the analytical solutions of Eqs. (7)(9) are double-checked by
comparing to their related numerical solutions of Eq. (6), which
is solved using a Raudau quadrature.
Eqs. (6)(9) are employed to study CO
2
permeation/sorption
data measured on the KP800 CMS membrane. As the experi-
mental data reect only the overall properties (the contributions
of blind pores as well as through pores), the isotherm model
and time-lag model are tted simultaneously to the experimen-
tal data at the same temperature.
3. Experiment
High-pressure sorption and permeation (upto 40 atm) data
were measured for pure CO
2
and N
2
gases on a CMS mem-
brane (referred to as KP800) derived from vacuum pyrolysis of
Table 1
The properties of the CMS membrane (KP800)
Pyrolysis temp. (

C) Density (g/cm
3
) Thickness (m) Pore size range (

A) Perm-selectivity
P
He
/P
CO
2
P
He
/P
N
2
P
He
/P
CF
4
800 1.99 125 <12 (N
2
adsorption) 0.67 22.28
<8 (molecular probe)
polyimide. The N
2
permeation data are newly reported but the
experimental rigs and procedures are same as those in the ref-
erences (Wang et al., 2001, 2007). The properties of the mem-
brane are listed in Table 1.
The perm-selectivities were calculated from the pure gas
permeabilities at room conditions. The pore size distributions
(PSDs) of the sample were determined in previous studies by
the molecular probe (Suda and Haraya, 1997) and N
2
sorption
(at 308, 333, and 363 K; Nguyen et al., 2003), respectively, and
were shown in Fig. 2.
4. Results and discussion
Fig. 3a shows the CO
2
sorption isotherm data (dots) mea-
sured on KP800 at three temperatures (308, 333, and 363 K).
The pressure readings of CO
2
have been converted to fugac-
ity using the acentric factor. Also shown in the gure are
the optimal ttings of the dual-Langmuir isotherm (solid line)
and Langmuir isotherm(dashed line, for the data of 308 Konly).
It is seen that the dual-Langmuir isotherm ts the data better
than the simple Langmuir equation. The tting parameters are
listed in Table 2.
The optimal isotherm parameters indicate that the sorption
capacity of the membrane sample mainly resides in the blind
pores with C
B
s
/C
T
s
7 and b
B
/b
T
5, which are relatively
stable at the three temperatures. The high capacity of blind
pores is a reasonable conjecture because the sieving (through)
pores are generally small apertures with high perm-selectivity
(33 for CO
2
/N
2
pair on KP800). Other study also pointed to
the possibility that sorption pores may dominate the capacity in
CMS membranes for sorptive species (Steel and Koros, 2005).
The blind pore character of KP800 can also be deduced from
its PSDs. We can see in Fig. 2 that N
2
sorption gives an upper
pore size range of 11

A (Nguyen et al., 2003), while the
molecular probe, which employs sorptive species of various
diameters (CO
2
, C
2
H
6
,n-C
4
H
10
, and i-C
4
H
10
) to probe the
sample for their capacities, only detects pore size upto 8

A.
This difference may suggest that a portion of large blind pores
are embedded in the membrane matrix and inaccessible to large
K. Wang / Chemical Engineering Science 62 (2007) 36543659 3657
A
4 6 8 10 12
m
m
o
l
/
g
/
A
0.00
0.02
0.04
0.06
0.08
0.10
0.12
KP800
M
i
c
r
o
p
o
r
e

v
o
l
u
m
e

(
c
c
/
g
)
0.00
0.05
0.10
0.15
0.20
0.25
<7.3A
7.3-7.7A
Fig. 2. The pore size (volume) distributions of KP800 sample derived from
N
2
adsorption (left) and molecular probes (right).
probe molecules due to the sieving effect of smaller through
pores. Permeation experiments further revealed that CF
4
(with
the diameter of 4.7

A) is not permeable on the KP800 sam-
ple while i-C
4
H
10
(with the diameter of 5

A) is marginally
adsorbing (Suda and Haraya, 1997). These experimental results
give the qualitative evidence that the critical diffusion path of
the sieving pores must be much smaller than 8

A to present a
selectivity of 33 for CO
2
(3.3

A)N
2
(3.68

A) pair, and justify
the existence of blind pores.
Fig. 3b shows CO
2
permeation time lag (dots) measured
at various permeation pressures and at 308, 333, and 363 K,
respectively. The dashed line is the model prediction by
Eq. (7a), which assumes a simple Langmuir isotherm and a
Darken relation for the apparent diffusion coefcient (with-
out blind pore character). It is seen that the Darken relation
considerably underestimates the pressure dependence of the
experimental time lag. The solid lines in Fig. 3b represent the
optimal ttings of the model with the blind pore character [Eq.
(6) or Eqs. (8)]. The optimal diffusion coefcients are listed in
Table 2. It is seen that the strong pressure dependence of the
time-lag data (diffusion anomaly) is adequately accounted for
by the blind pore character. The ratio k =b
B
/b
T
5 suggests
that the blind pores are dominant in the overall time lag. Com-
putation results reveal that the time lag in blind pores (L
B
)
constitutes about 90% of the overall time lag and this ratio
increases slightly at the higher end of permeation pressure.
Fig. 4 shows the parametric study of the normalized time
lag of blind pores (L
B
normalized with respect to its value
at the lowest experimental permeation pressures, L
B1
). The
simulation starts with CO
2
isotherm parameters at 308 K (k
6, listed in Table 2). Then the ratio of k varies from 6 to 0.6
while other parameters are kept as constants. The curve with
k=1 corresponds to the Langmuir equation and Darken relation
[Eq. (7a), without blind pore character]. We see that the time
lag in blind pores presents stronger pressure dependence than
the Darken relation when k >1, and shows weaker pressure
dependence than the Darken relation when k <1.
This phenomenon can be well interpreted by the blind pore
character. When k >1, the blind pores will sink increasingly
Fugacity (kPa)
0 500 1000 1500 2000 2500 3000 3500 4000
A
m
o
u
n
t

a
d
s
o
r
b
e
d

(
m
m
o
l
/
g
)
0
1
2
3
4
5
308K
333K
363K
Dual Langmuir
Langmuir
Fugacity (kPa)
0 300 600 900 1200 1500 1800 2100
T
i
m
e

L
a
g

(
s
)
0
300
600
900
1200
1500
308K
333K
363K
Without blind pores, LB=0
Fig. 3. (a) CO
2
isotherm on KP800 CMS membrane (dots). : the
dual-Langmuir equation; - - -: simple Langmuir isotherm (C
s
=4.59 mmol/g,
b=1.1610
2
kPa
1
). (b) CO
2
permeation time lag on KP800 CMS mem-
brane (dots). : time-lag model with blind pore characters [Eqs. (7)(9)];
: time-lag model with Darken relation only (D
0

=1.56 10
8
cm
2
/s).
more diffusing species than the through pores as the permeation
pressure increases, due to the higher afnity and non-linearity
of the isotherms inside. Consequently, a much higher diffusion
ux (and subsequently a higher diffusion coefcient) is required
for the system to reach the steady state at the xed time interval.
For example, the model without blind pore character predicts a
diffusion coefcient of 5.55 10
9
cm
2
/s (Wang et al., 2007)
for CO
2
permeation data at 308 K on KP800. Therefore, even
as the Fickian diffusion still holds in the through pores, the
overall time lag presents a much stronger dependence on the
permeation pressure. The opposites are true when k <1.
Fig. 5a shows N
2
sorption isotherm data (dots) and the t-
tings (lines) of the dual-Langmuir isotherm. The isotherm data,
which were used to derive the PSD of the sample (Nguyen
et al., 2003), include both the adsorption and desorption data.
Fig. 5b presents the permeation time lag (dots) of N
2
mea-
sured at 308, 333, and 363K, respectively. Also shown in the
same gure are the ttings of the model (lines) with blind pore
character. The derived isotherm parameters and diffusion coef-
cients are listed in Table 2. It is seen that the dual-Langmuir
model ts the isotherm data well. The time-lag model, however,
3658 K. Wang / Chemical Engineering Science 62 (2007) 36543659
Table 2
The optimal isotherm parameters and diffusion coefcients
Temperature (K) C
B
s
b
B
C
T
s
b
T
D
0

(mmol/g) (kPa
1
) (mmol/g) (kPa
1
) (cm
2
/s)
308 CO
2
4.12 1.18 10
2
0.636 1.80 10
3
5.24 10
7
N
2
0.204 1.63 10
3
9.17 10
2
1.39 10
4
9.26 10
8
333 CO
2
3.73 7.18 10
3
0.542 1.39 10
3
9.37 10
7
N
2
0.182 1.07 10
3
7.52 10
2
1.15 10
4
1.84 10
7
363 CO
2
3.30 3.74 10
3
0.539 8.32 10
4
1.18 10
6
N
2
0.155 7.71 10
4
7.13 10
2
7.79 10
5
2.26 10
7
Fugacity (kPa)
400 800 1200 1600 2000
N
o
r
m
a
l
i
z
e
d

t
i
m
e

l
a
g
0.2
0.4
0.6
0.8
1.0
k=0.6
0.8
2
4
6
1
Fig. 4. The normalized permeation time lag of blind pores (L
B
/L
B1
) at
various ratio of k =b
B
/b
T
.
underestimates the pressure dependence of the time lag at the
low end of permeation pressure. This trend is more obvious at
the higher temperature (whereas the isotherm is more linear).
Compared with CO
2
, N
2
is a weakly adsorbing species and
its isotherm linearity is high. As discussed earlier, the pressure
dependence of the time lag in blind pores, L
B
, is dominated
by the k ratio. However, the k ratio cannot increase indenitely
to match the pressure dependence of the time-lag data as it is
constrained by the shape (linearity) of the isotherm. Therefore,
for adsorbing species with non-linear isotherm like CO
2
, the
blind pore character alone is able to cope with the diffusion
anomaly. For weakly adsorbing species like N
2
, however, the
model is insufcient to account for the diffusion anomaly over
the wide range of permeation pressure. This observation sug-
gests that, even as blind pore character does exist and plays
an important role in the diffusion anomalies observed on the
CMS membrane, other structural heterogeneity factors such as
the pore connectivity, partially blind pores, interaction among
the adsorbed phase, etc. may also play some parts. Therefore,
more experimental evidences are needed to quantify the con-
tributions of these factors.
The mathematical derivations/analysis of the permeation
time lags with blind pore character are based on the structural
model of the CMS membrane, which is adapted from the early
Fugacity (kPa)
0 1000 2000 3000 4000 5000
A
m
o
u
n
t

a
d
s
o
r
b
e
d

(
m
m
o
l
/
g
)
0.00
0.05
0.10
0.15
0.20
0.25
308K
333K
363K
Fugacity (kPa)
0 300 600 900 1200 1500 1800 2100
T
i
m
e

L
a
g

(
s
)
1000
2000
3000
4000
5000
6000
7000
8000
308K
333K
363K
Fig. 5. (a) N
2
isotherm on KP800 CMS membrane (dots). : the
dual-Langmuir equation. (b) N
2
permeation time lag on KP800 CMS mem-
brane (dots). : time-lag model with blind pore character [Eqs. (7)(9)].
model of Goodknight and Fatt (1961). In comparison, Ashs
model is more realistic in that it assumes that blind pores con-
tribute partly to the overall ux and this ux is a function of
time (Ash et al., 1963). However, the time-dependent compo-
nent is difcult to model and even difcult to measure. The
approach of Petropoulos et al. has the merits of analyzing time
lags of different modes, which certainly contain more insight-
ful information. Their ndings (contribution of blind pores is
minimal), however, are in no contradiction with this study,
K. Wang / Chemical Engineering Science 62 (2007) 36543659 3659
because their conclusions are based on the permeation of
weakly adsorbing species (He, Ne, and N
2
) in pellets formed
by multi-step compactions (Galiatsatou et al., 2006). This study
shows that the blind pores will sink very little such species
and their effects on the overall time lag could be minimal at
the low pressure end. It is also noted that the permeation time
lag of He and H
2
can hardly be detected on KP800 membrane
at the room temperature/pressure. Even as the time lag of N
2
could be signicant in their pellets (Galiatsatou et al., 2006),
the sorptivity is very low at their experimental permeation
pressure of 15 kPa.
The KP800 CMS membrane was produced via the direct
vacuum pyrolysis of a polymer. In comparison, a commercial
CMS is generally produced from low-grade carbonaceous pre-
cursors (e.g., coals, nutshells, etc.) with chemical vapor depo-
sition process to ne-tune the sizes of pore mouths. Therefore,
strong diffusion barrier (of pore mouths) is commonly observed
on such commercial CMSs during the measurement of tran-
sient uptakes in a batch adsorber (Rutherford et al., 2003; Ding
et al., 2005). To minimize the effect of possible surface barriers
on the time-lag measurement, cells with large volumes were
used in both upstream and downstream gas reservoirs for the
system to reach the pseudo-steady state.
The time-lag model and isotherm model together have ve
parameters to be optimized with respect to two sets of exper-
imental data (isotherm and time lag) at the same temperature.
Theoretically, many local minimums exist and it is difcult to
ensure a global solution. However, k ratio has been found to
be the most critical parameter and its value is restricted by the
pressure dependence (or linearity) of the isotherm as well as
the time lag. Other parameters (such as the capacities and diffu-
sion coefcient) are virtually lumped together to inuence the
magnitude of the overall properties. As the result, the param-
eters listed in Table 2 are found to be stable after many trial
runs. It was noted that good initial inputs are required for the
model to converge correctly (this is achieved by many trials
aided with visual judgment. Negative values may be obtained
with arbitrary inputs). Considering the complexity of the mi-
croporous network of a CMS membrane and the simplicity of
the dual-Langmuir isotherm, the optimal values listed in Table
2 should be treated as being more qualitative than quantitative.
Nevertheless, the blind pore character, which is the structural
characteristics of the membrane as indicated in the PSD of the
sample, is well represented by the isotherm and the time-lag
models developed in this study. These models offer a new per-
spective for the study of diffusion anomalies commonly ob-
served on such materials.
5. Conclusion
The blind pore character is the structural property of a
CMS membrane and the major source of the observed diffu-
sion anomalies. The time-lag analysis showed that the size
(or afnity) difference between the blind pores and through
pores dominates the concentration dependence of the appar-
ent diffusion coefcient. The model developed compares well
with CO
2
permeation data measured on a polymer-based CMS
membrane under various experimental conditions. However, the
model underestimates the pressure dependence of N
2
data at
the low end of permeation pressure and this may point to the
existence of other heterogeneity factors.
Acknowledgment
This research is supported by the Academic Research Fund
(AcRF), Nanyang Technological University and Ministry of
Education, Singapore.
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