Journal of Membrane Science 330 (2009) 5156

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Journal of Membrane Science
j our nal homepage: www. el sevi er . com/ l ocat e/ memsci
A new sorption model with a dynamic correction for the determination of
diffusion coefcients
Ond rej Vopi cka

, Vladimir Hynek, Miroslav Zga zar, Karel Friess, Milan

Spek
Institute of Chemical Technology, Department of Physical Chemistry, Technick 5, Prague 6, 166 28, Czech Republic
a r t i c l e i n f o
Article history:
Received 8 July 2008
Received in revised form
13 November 2008
Accepted 21 December 2008
Available online 30 December 2008
Keywords:
Diffusion coefcient
Dynamic correction
Vapor sorption
Laplace transform
Cellulose-based membranes
a b s t r a c t
This paper describes animprovement to the method used for the calculationof diffusioncoefcients from
data obtained by the measurement of vapor sorption kinetics in a at, non-porous polymeric membrane.
The advantage of our corrected model is that it can be applied to systems displaying both fast and slow
sorption kinetics, as is demonstrated using cellulose myristate hexane and cellulose acetovalerate
ethanol systems at a temperature of 298K. Experiments were conductedona speciallydevelopedsorption
apparatus equipped with McBains spiral quartz balances. Sorption kinetics are generally described by
the solution of Ficks second law, the solution of which assumes relative pressure in the form of the unit
step function. Our correction involves modifying this solution so that a more realistic relative pressure
increase is assumed in terms of the Laplace transform.
2008 Elsevier B.V. All rights reserved.
1. Introduction
The transport of a vapor in a at, non-porous polymeric
membrane has frequently been described in terms of the
solutiondiffusion model, [1]. This model posits that the trans-
port process can be divided into three sub-processes; namely, the
sorption of the penetrant into the membrane, diffusion through
the membrane, and desorption. This type of transport is typically
described in terms of permeability, solubility and diffusion coef-
cients. The gravimetric sorption method enables us to determine
the sorption and diffusion coefcients for a pure vapor in a poly-
meric membrane, and to estimate the appropriate permeability
coefcients, [1,2]. This paper focuses on determining the diffusion
coefcients of vapors when sorbate pressure changes over time.
2. Theoretical part
2.1. Objective
The gravimetric sorption method involves measuring the mass
of vapor sorbed in a polymer membrane as a function of time until
a constant value is reached at equilibrium. Prior to the start of such
experiments, absolute pressure is effectively equal to zero and the
membrane does not contain any vapor. During these experiments

Corresponding author. Tel.: +420 220444029.

E-mail address: Ondrej.Vopicka@vscht.cz (O. Vopi cka).
a constant temperature is maintained and the pressure of the pure
vapor equals that of the pressure selected for the experiment. The
relative pressure is described using the unit step function:
p()
p

=
_
0 if 0
1 if > 0
, (1)
where p() denotes the dependence of vapor pressure on time and
p

= lim

(p()) is vapor pressure at sorption equilibrium. In the

literature [3,4], the solution of Ficks second law for sorption in a
at sheet membrane assuming a constant diffusion coefcient has
been described as follows:
Q()
Q

= 1
8

2

i=N

i=0
1
(2i +1)
2
exp
_

2
D (2i +1)
2
l
2
_
, (2)
where N , Q() is the amount of vapor sorbed by the mem-
brane, Q

is the amount of vapor sorbed at sorption equilibrium,

l denotes the thickness of the membrane and D is the constant
diffusion coefcient. In reality, however, the relative pressure of
vapor during a sorption experiment does not follow Eq. (1) exactly.
Therefore, the boundary conditions assumed in Eq. (2) are also not
satised. However, this discrepancy becomes insignicant when
the kinetics of relative pressure increase (i.e. when the vapor is
released into the evacuated volume containing the membrane)
are much faster than the sorption process itself. Eq. (2) can be
corrected to obtain a more general formula for the calculation
of diffusion coefcients. Solutions to similar problems have been
described in the literature [3,57].
0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.12.037
52 O. Vopi cka et al. / Journal of Membrane Science 330 (2009) 5156
2.2. Correction I
The aim of correcting the initial solution Eq. (2) is to involve a
more realistic model of relative pressure increase.
Let x
1
() be an input function and y
1
() be the output function
of the system assigned to the input function. Assume that we are
looking for a new output function y
2
() for the same (physical)
system assigned to a new input function x
2
(), which is known.
If all the above mentioned functions satisfy the assumptions of the
Laplace transform(see Appendix, A), we can dene X
1
(s) = L{x
1
()}
and Y
1
(s) = L{y
1
()}, where s is a complex variable and L denotes
the Laplace transform. Then we can state Y
1
(s) = X
1
(s) H(s), and
the system function H(s) can be expressed. The new output func-
tion takes the formy
2
() = L
1
{H(s) X
2
(s)}, where L
1
denotes the
inverse Laplace transform.
This general approach allows us to incorporate additional
dynamics into the model of the process being described. Non-
instantaneous pressure increase is incorporated in the model of
sorption kinetics.
In this paper, Eq. (2) is the output function assigned to input
functionEq. (1), andwe are lookingfor a newoutput functionlinked
to the following new input function:
p
cI
()
p

=
_
0 if 0
1 exp(a) if > 0
(3)
where p
cI
() is the vapor pressure dependence on time assumed in
Correction I, and a is a real positive parameter denoting the inverse
value of the time constant. The Laplace transform, [8,9] of Eq. (3)
can be expressed as
L{p
cI
()}
p

=
1
s

a
s +a
. (4)
The Laplace transform of Eq. (1) has the form
L{p()}
p

=
1
s
. (5)
For a nite value of nonnegative integer N and assuming > 0,
the Laplace transform of Eq. (2) can be expressed in the following
form:
L{Q()}
Q

=
1
s

8

2

i=N

i=0
1
(2i +1)
2

l
2

2
D (2i +1)
2
+s l
2
. (6)
Eq. (6) is the product of the Laplace transformof the input func-
tion Eq. (5) and the system function. When the system function is
expressedandmultipliedby the Laplace transformof the newinput
functionEq. (4), the Laplace transformof the correctedequationcan
be formulated thus:
L{Q
cI
()}
Q

=
_
1
s

8

2

i=N

i=0
1
(2i +1)
2

1
s +d (2i +1)
2
_

_
a
s +a
_
,
(7)
where
d =

2
D
l
2
. (8)
Assuming that a / = d (2i +1)
2
for any integer 0 i N, andthat
> 0, the inverse Laplace transform of Eq. (7) can be expressed in
the following form:
Q
cI
()
Q

= 1 exp(a)
8

2

i=N

i=0
_
1
(2i +1)
2

a
d (2i +1)
2
a

_
exp(a) exp((2i +1)
2
d )

_
. (9)
When < 0, this equation is identically equal to zero. Provid-
ing that the value of parameter a has already been evaluated, Eq.
(9) can then be used to calculate the diffusion coefcient from the
experimental sorption kinetic data.
As mentionedinSection2.1, theunit stepfunctiondoes not accu-
rately describe the real relative pressure increase. This discrepancy
cannot be ignored when the vapor sorption rate becomes faster,
and approaches the velocity of the relative pressure increase. The
ratio of sorption velocity to relative pressure increase is measured
using the a/d ratio. When a/d , no correction is needed. In the
literature [3], a solutionequivalent toEq. (9) has beenderivedunder
time-dependent boundary conditions similar to those described in
Eq. (3). Both solutions converge to the same function as Nincreases.
The advantages of correcting the initial solution Eq. (2) are that
there is no need to solve Ficks second law for each model of rela-
tive pressure increase, and that it becomes possible to incorporate a
model of mass sensor dynamic response (e.g. Cahn microbalances)
into the sorption kinetics model.
2.3. Correction II
In Correction I the dependence of relative pressure on time was
assumed in the formof Eq. (3). However, the dependence of relative
pressure on time during sorption experiments is more accurately
expressed as
p
cII
()
p

=
_
0 if 0
1 exp() exp() if > 0
(10)
where p
cII
() is the vapor pressure dependence on time assumed in
Correction II, and is a real positive parameter. The Laplace trans-
form of this equation takes the form
L{p
cII
()}
p

=
1
s


2
(s +)
2
. (11)
As in Section 2.2, we thus obtain the Laplace transform of the
corrected equation:
L{Q
cII
()}
Q

=
_
1
s

8

2

i=N

i=0
1
(2i +1)
2

1
s +d (2i +1)
2
_
s

_
1
s


2
(s +)
2
_
. (12)
Assuming that > 0, and that / = d (2i +1)
2
for any integer
0 i N, the corrected model can be expressed thus:
Q
cII
()
Q

= 1 exp() exp()
8

i=N

i=0
_
1
(2i +1)
2
_
A exp(d (2i+1)
2
)+(C A) exp()
_
_
,
(13)
where
A =

2

2
2d (2i +1)
2
+d
2
(2i +1)
4
(14a)
C =

2
d (2i +1)
2

(14b)
Providing that the value of parameter has already been eval-
uated, the diffusion coefcient can be calculated by tting Eq. (13)
to the experimental sorption kinetic data.
O. Vopi cka et al. / Journal of Membrane Science 330 (2009) 5156 53
Fig. 1. Approximation of relative pressure increase obtained using Correction I pres-
sure model: cellulose myristatehexane; 298K; p =5.458kPa.
2.4. Experimental data tting
Prior to the start of each experimental run, data recording was
initiated manually. Therefore, there was some delay between the
start of data recording (zero time) and the start of the pressure
increase. To reect this Eq. (3) had to be modied thus:
p
cI
(t)
p

=
_
0 if t b 0
1 exp(a (t b)) if t b > 0
, (15)
where b is the time delay and t is the time recorded by the
apparatus. The values of the parameters a and b were determined
usingtheGaussNewtonoptimizationmethod[10]. Fig. 1shows the
approximation for the relative vapor pressure data obtained using
Eq. (3).
The GaussNewton method was used to calculate the diffusion
coefcient using Eq. (9), in which the substitution = t b was
employed. The diffusion coefcient was also calculated using Eq.
(2), in which the same substitution was made. Figs. 2 and 3 show
the approximations for the relative sorbed amount data obtained
using Eqs. (2) and (9), respectively. These models and the measured
Fig. 2. Approximation of sorption kinetic data using uncorrected sorption model:
cellulose myristatehexane; 298K; p =5.458kPa.
Fig. 3. Approximation of Correction I sorption model to sorption kinetic data: cel-
lulose myristatehexane; 298K; p =5.458kPa.
data are plotted against the square root of time in Fig. 4, the initial
nonlinearity of the corrected model being caused by the pressure
correction.
When Correction II is used, Eq. (10) must be changed as follows:
p
cII
(t)
p

=
_
0 if t 0
1exp( (t)) (t) exp( (t )) if t > 0
(16)
The GaussNewton method was used to calculate the values of
and from the measured pressure increase, the rst estimation
of the time delay being determined using a method developed
by Strejc [11], i.e. b
0.1
a
. Fig. 5 shows the approximation for
the relative pressure increase data obtained using Eq. (10). The dif-
fusion coefcient was calculated by optimizing Eq. (13)(with the
Fig. 4. Approximation of both Correction I (blue solid line) sorption model and
uncorrected model (red dashed line) to sorption kinetic data: plotted against square
root of time; cellulose myristatehexane; 298K; p =5.458kPa. (For interpretation
of the references to color in this gure legend, the reader is referred to the web
version of the article.)
54 O. Vopi cka et al. / Journal of Membrane Science 330 (2009) 5156
Fig. 5. Approximation of relative pressure increase obtained using Correction II
pressure model: cellulose myristatehexane; 298K; p =5.458kPa.
substitution = t ) to the sorption kinetic data. Fig. 6 shows the
approximation for the relative sorbed amount data obtained using
Eq. (13). Fig. 7shows the Correction I sorption model, the Correc-
tion II sorption model and the measured data plotted against the
square root of time. Integer N equals 5 in these approximations.
Correction I assumes a / = d (2i +1)
2
and Correction II assumes
/ = d (2i +1)
2
for 0 i N; assumptions which must be checked
during the GaussNewton processes.
We evaluated the 95% condence intervals for the diffusion
coefcients in two steps; (i) we used the Bonferroni method [10]
to determine the discrepancy of the model from the measured
datasuch condence intervals D D
t
serve as a measure of
quality of t; (ii) the 95% condence intervals were recalculated in
respect to the variability inthickness. The appropriate relative devi-
ations were approximately 14% for the cellulose myristatehexane
system, and 9% for the cellulose acetovalerateethanol system.
Figs. 8 and 9 plot the diffusion coefcients and 95% condence
intervals against the equilibrium vapor pressures. Tables 1 and 2
list the equilibriumvapor pressures, a/d ratios, calculated diffusion
coefcients and D
t
values.
Fig. 6. Approximation of Correction II sorption model to sorption kinetic data: cel-
lulose myristatehexane; 298K; p =5.458kPa.
Fig. 7. Approximation of Correction I (blue solid line) and Correction II (red dashed
line) sorption models to sorption kinetic data: plotted against square root of time;
cellulose myristatehexane; 298K; p=5.458kPa. (For interpretation of the refer-
ences to color in this gure legend, the reader is referred to the web version of the
article.)
Fig. 8. Dependence of diffusioncoefcients onequilibriumpressure of hexane vapor
at 298K in the cellulose myristate membrane (error bars of 14% show the 95% con-
dence interval).
Fig. 9. Dependence of diffusion coefcients on equilibrium pressure of ethanol
vapor at 298K in the cellulose acetovalerate membrane (error bars of 9% show the
95% condence interval).
O. Vopi cka et al. / Journal of Membrane Science 330 (2009) 5156 55
Table 1
Results of tting of uncorrected model and corrected models to sorption kinetic data, cellulose myristatehexane.
p (kPa) a/d 10
12
Dcor. II (m
2
s
1
) 10
12
D
t
cor. II
(m
2
s
1
) 10
12
Dcor. I (m
2
s
1
) 10
12
D
t
cor. I
(m
2
s
1
) 10
12
Dno cor. (m
2
s
1
) 10
12
D
t
no cor.
(m
2
s
1
)
1.271 4.9 29 2 30 2 18 2
2.839 3.4 34 1 35 1 20 2
4.542 3.4 36 1 37 1 19 2
5.458 5.2 38 1 39 1 24 2
8.547 3.5 41 2 42 2 26 2
10.668 5.1 45 3 46 3 29 3
11.633 5.3 48 3 48 3 32 3
Table 2
Results of tting of uncorrected model and corrected models to sorption kinetic data, cellulose acetovalerateethanol.
p (kPa) a/d 10
15
Dcor. II (m
2
s
1
) 10
15
D
t
cor. II
(m
2
s
1
) 10
15
Dcor. I (m
2
s
1
) 10
15
D
t
cor. I
(m
2
s
1
) 10
15
Dno cor. (m
2
s
1
) 10
15
D
t
no cor.
(m
2
s
1
)
0.713 62.3 343 3 344 3 334 3
1.396 100.5 308 4 309 4 300 4
1.975 80.0 417 4 417 4 403 5
2.583 85.5 413 5 414 5 403 5
3.208 64.6 544 6 545 6 523 6
3.907 46.7 594 8 595 8 561 9
4.682 98.4 584 9 585 9 572 9
5.157 80.2 651 8 652 8 634 8
5.632 65.1 611 8 612 8 589 8
3. Experimental part
3.1. Membranes and chemicals
Both membranes used were obtained from the Institute of
Macromolecular Compounds, Russian Academy of Sciences, St.
Petersburg, Russia: cellulose acetovalerate [12] with a thickness
of (35 2) m (95% condence interval of mean, normal distri-
bution) and a melting point of 170

C; cellulose myristate [13]

with a thickness of (100 7) m (95% condence interval of
mean, normal distribution) and a melting point of 130

C. Melting
points weremeasuredusingaSetaramDSC131differential scanning
calorimeter at temperature increases of 10

C per minute within

a temperature interval of 25300

C. Ethanol (ethanol absolute,

99.0100.0%, Merck) and n-hexane (min. 99.0%, Penta) were used
as obtained.
3.2. Apparatus
We used a self-constructed sorption apparatus [14,15] equipped
with McBains spiral quartz balances to measure the sorbed mass of
the compound in a polymer sample. The sorption of a vapor into a
polymer matrix results in the elongation of the quartz spiral, which
was monitored by a camera system specially developed by Neovi-
sion s.r.o., the Czech Republic. The absolute pressure of the pure
vapor was continuously measured by pressure gauges (Oerlikon
Leybold Vacuum GmbH, Germany).
A membrane was suspended on the end of the quartz balances
anddegassedat anabsolute pressure lower than1 Pa until the mass
of the sample remained constant over time. Prior to each measure-
ment, the membrane was degassed for approximately three times
longer thanthe time neededfor desorptionto the initial mass of the
degassed membrane. At the start of eachexperiment, the vapor was
introduced into the evacuated volume containing the membrane.
The valve separating the evacuated volume and the vapor container
was opened manually so that oscillation of the quartz spiral was
minimized. Therefore the parameters of the pressure increase (a
or ) were not constant and were calculated separately for each
experiment. The whole apparatus was maintained at 298 K for all
experiments.
4. Results and discussion
Fig. 8 plots the diffusion coefcients calculated for the cellu-
lose myristatehexane system against hexane equilibrium vapor
pressure. The a/d ratio for this system ranged from 3 to 5. Sig-
nicant differences between the diffusion coefcients calculated
by the corrected models and those obtained using the uncor-
rected model can be seen, thereby showing that our dynamic
correction is necessary when the a/d ratio approaches this
range.
Fig. 9 plots the diffusion coefcients calculated for the cellulose
acetovalerateethanol system against ethanol equilibrium vapor
pressure. The a/d ratio for this systemrangedfrom47to 101. No sig-
nicant differences can be seen between the diffusion coefcients
calculated by the corrected models and those obtained using the
uncorrected model. No correction is necessary when the a/d ratio
approaches this range.
Although the description of relative pressure increase in Cor-
rection I is assumed to be less accurate than that in Correction II,
Fig. 8(cellulose myristatehexane system) shows that the differ-
ences betweenthe diffusioncoefcients calculatedbythe corrected
models were negligible (compared to the differences between the
coefcients calculated by the corrected models and those obtained
using the uncorrected model).
5. Conclusions
Our correction method incorporates a more realistic pressure
increase into sorption kinetics using the Laplace transform and, at
the same time, removes the need to solve Ficks second law for
each pressure model. This was shown for two models of pressure
increase. According to Correction I, as the number of terms in the
series increases, the sorptionkinetics model converges to a solution
published by Crank [3].
Using cellulose myristatehexane and cellulose acetovalerate
ethanol systems, we have shown that the use of our correction
extends the applicability of the sorption model for the calculation
of diffusion coefcients to faster sorption processes. When sorp-
tion is slow in relation to pressure increase, both the corrected
models and the uncorrected model produced very similar diffusion
56 O. Vopi cka et al. / Journal of Membrane Science 330 (2009) 5156
coefcients, thereby alsoshowing that our models canbe usedeven
when no correction is strictly necessary.
Furthermore, this approach makes it possible to incorporate the
additional dynamics of a slowly responding mass sensor (e.g. Cahn
microbalances). Indeed, more than one additional dynamics can be
incorporated in an initial model.
Acknowledgment
This work was supported by grant research project MSM
6046137307 of the Czech Ministry of Education, Youth and Sports.
Appendix A. Laplace transform
The Laplace transform of the function f () is dened as
L{f ()} =

_
0
f () exp(s)d, (A.1)
where s is a complex variable and L denotes the Laplace transform.
The function f () is assumed to be piecewise continuous, where all
points of discontinuity are isolated and the function approaches a
nite limit fromeach side of the point of discontinuity, and f () = 0
for < 0. It is also assumed that our function f () is of exponential
order
0
so that
lim

f () exp() = 0 (A.2)
when >
0
. If we assume an exponential order function, we
can nd M and for > T
0
so that
|f ()| < Mexp(). (A.3)
Functions occurring in the solution for the time responses of
stable linear systems are of exponential order 0. The general treat-
ment shown in Section 2.2 is based on the Laplace transformof the
convolution integral.
If x() and h() are piecewise continuous functions of exponen-
tial order and x() = h() = 0 for < 0, the convolution integral is
dened as follows
y() =

_
0
x(t)h( t)dt, (A.4)
where y() is a piecewise continuous function of exponential
order and y() = 0 for < 0. The Laplace transformof the convolu-
tion integral is thus given by
L{y()} = X(s)H(s) = H(s)X(s), (A.5)
where X(s) = L{x()} and H(s) = L{h()}. All functions used in
this article meet the requirements of the Heaviside expansion the-
orem, which was used to obtain inverse Laplace transforms. For
a more general treatment of the Laplace transform the reader is
referred to the literature [8].
Nomenclature
A dened by Eq. (14a)
a real positive parameter dened in Eq. (3) [s
1
]
b the time delay dened in Eq. (15) [s]
C dened in Eq. (14b) [s
1
]
d dened in Eq. (8) [s
1
]
D diffusion coefcient m
2
[s
1
]
D
t
deviation of the diffusion coefcient (see Section
2.4) m
2
[s
1
]
time delay dened in Eq. (16) [s]
H(s) system function (see Section 2.2)
i integer
l thickness of at membrane m
L Laplace transform operator
L
1
inverse Laplace transform operator
N nonnegative integer
p() dependence of absolute pressure any pressure unit
p

= lim

(p()) the same as p()

p
cI
() assumed pressure dependence Eq. (3) the same as
p()
p
cII
() assumed pressure dependence [Eq. (10)] the same
as p()
Q() mass of sorbed vapor dependent on time any mass
unit
Q

= lim

(Q()) The same as Q()

Q
cI
() corrected sorbed mass dependence [Eq. (7)]the
same as Q()
Q
cII
() corrected sorbed mass dependence [Eq. (12)]the
same as Q()
s complex variable [s
1
]
time [s]
t time recorded by the apparatus (see Section 2.4) [s]
real positive parameter dened in Eq. (10) [s
1
]
x
1
() example input function (see Section 2.2)
X
1
(s) Laplace transform of x
1
()
x
2
() example input function (see Section 2.2)
y
1
() example output function (see Section 2.2)
Y
1
(s) Laplace transform of y
1
()
y
2
() example output function (see Section 2.2)
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