Chapter 2

Transport through polymer

membranes
In this chapter I will give a short introduction in the process of transport
through membranes, concentrating on the gas phase/rubbery polymer system.
The transport from the gas phase through rubbery polymers can be described
by the solution-diffusion model, which will be outlined in this chapter. Also
a brief look at the experimental measurement of the permeability by means of
the time-lag method and some interesting industrial applications are given.

2.1 The polymer matrix

Before looking at the mechanism of gas transport through membranes it is necessary
to consider some features of the two principal microstructural conditions of polymeric
material, the glassy and rubbery state.
It has been known for a long time that the mechanism of diffusion is very different in
rubbery and glassy polymers. This is mainly due to the fact that glassy polymers are not
in a true state of equilibrium. The difference in mechanism is reflected in the significant
differences observed in the dependence of the diffusion coefficient, as well as the
permeability and solubility coefficients, on the penetrant gas pressure or concentration
in polymers and on the temperature [8]. For example, the diffusion coefficients for light
gases in rubbery polymers are often independent of concentration. By contrast, in glassy
polymers the diffusion coefficients are highly nonlinear functions of concentration and
reach a constant value at sufficiently high concentration.
At temperatures below the glass transition temperature Tg the polymer is in its glassy
state and is hard and may be brittle, which is directly related to the restricted chain
mobility. The intermolecular forces between the chains do not allow other movement
5

Transport through polymer membranes

than vibrations. All structural properties as the distribution of cavities in the polymer
have effectively become static quantities. Depending on the conditions during the
formation of the glassy state (for example, the temperature gradient) the polymer is
more or less trapped in a non-equilibrium state. In glassy polymers the penetrant
diffusion is low but size selectivity is very good.
Above the glass transition temperature the polymer is in its rubbery state. In this state the
polymers are generally tough and flexible, which is associated with freer chain motion.
Rubbery polymers have very short relaxation times (compared to glassy polymers) and
respond very rapidly to external stresses. Thus a change in temperature causes an
immediate adjustment to the new equilibrium state. A similar immediate adjustment
occurs when small penetrants are absorbed in a rubbery polymer. Larger segments of
the polymer are thought to participate in the penetrant diffusion process due to internal
chain motions such as chain rotations, translations and stronger vibrational motions.
The penetrant diffusion is much faster than in a glassy polymer but size selectivity is
lower.
In both the glassy and rubbery state the polymer properties can be further modified
by the presence of crystalline phases, by stress induced orientations or as a function
of cross-link density. They tend to place additional constraints on the mobility of the
amorphous phase through which diffusion takes place. (It is partly because of these
possible variations in polymer properties that there is such a wide range in experimental
values of permeability coefficients)

Gas versus liquid permeation

Permeation through polymer membranes can occur from both the gas and the liquid
phase. In gas permeation diffusion coefficients are independent of penetrant concentration in the membrane in contrast to vapor or liquid permeation. There the membrane may
be highly swollen by a penetrating liquid. This opens up the structures with the result
that the absolute flux rates through the membrane can be 2 or 3 orders of magnitude
larger than for a (noncondensible) gas. Thus in vapor or liquid permeation the diffusion
coefficients are strong (typically exponential) functions of concentration.
For vapor and liquid separation different theories have been used, for example: irreversible thermodynamics, preferential sorption-capillary flow theory or the solutiondiffusion mechanism. But in permeation from the gas phase the picture is simpler and
only the solution-diffusion mechanism is used.
As the process of permeation from vapor or liquid phases involves many extra difficulties
I will limit myself to the permeation of small molecules from a gaseous phase. And
even though polymers are used for various permeation processes in both their rubbery
and glassy state, we shall concentrate on the permeation process in polymers in their
rubbery state only. Thus in this thesis I shall express the transport properties in the cast

2.2 Solution-diffusion mechanism

of the solution-diffusion picture.

2.2 Solution-diffusion mechanism

The first to use the term solution-diffusion mechanism was Graham [9] in 1866. He
postulated that the penetrant leaves the external phase by dissolving in the membrane.
It then undergoes molecular diffusion in the membrane, driven towards the downstream
face by for example a concentration or pressure gradient, after which it evaporates again
in the external phase. Thus the permeability coefficient P , defined by the ratio between
the flux J of the permeant species and its concentration gradient c over the membrane
of thickness d

J = P dc

:1)

(2

is given by the product of the diffusion coefficient D and a solubility factor S

P = DS

:2)

(2

A postulate of which the theoretical foundation will be shown next.

In the solution-diffusion model we consider an isothermal homogeneous stationary
membrane in which particles at a position r are dissolved with a local concentration
c(r). The particle flux J is assumed to behave in the regime of a linear irreversible
process with the gradient of the chemical potential as the driving force. The flux is given
by

J (r) = c(r)v(r)

:3)

(2

where v (r) is the average velocity of the dissolved particles. In the linear regime v (r )
can be written as

v(r)

=
=

 F th
, 1 r(r)
1

where F th is the thermodynamic force,  a friction coefficient and

potential of the dissolved particles. The latter can be written as

(r) = 0 + RT ln c(r) + ex(r)

:4)

(2

 the chemical
:5)

(2

Transport through polymer membranes

Phase 1

Polymer Membrane
c1

Phase 2
c2

ex

Figure 2.1: The schematic polymer membrane. The membrane separates two phases with
concentrations c1 and c2 and chemical potential 1 and 2 . We assume that  is continuous
at the interface and that ex (the excess chemical potential) is constant throughout the
homogeneous membrane.

in which 0 is the standard chemical potential of the ideal gas phase based on unit molar
concentration, c is the local concentration and ex (r) is the excess chemical potential of
the dissolved species with respect to the ideal gas state. Equations 2.3, 2.4 and 2.5 give

c(r) r (r):
J (r) = ,RT
r
c
(r ) ,
ex



:6)

(2

Equating RT= with the diffusion coefficient D , eq. 2.6 can be written as

J (r) = ,D

exp(,ex (r)=RT )
r fc(r ) exp(ex (r )=RT g :

:7)

(2

Equation 2.7 is still general. We now consider a membrane with thickness d in the
x-direction and infinite dimensions in the yz-plane. The interfaces at x = 0 and x = d
are in contact with concentrations c1 and c2 (c = c2 , c1 ) and we assume that an
ideal gas phase is in equilibrium across both interfaces. Hence  is continuous at the
interfaces. Furthermore ex is assumed to be constant throughout the homogeneous
membrane. This implies that any concentration dependence of ex is neglected. Thus

2.3 Experimental measurement of permeabilities.

0 + RT ln c1 = 0 + RT ln c(0) + ex

:8)

(2

or

c(0) = c1

exp(,ex =RT )

c(d) = c2

exp(,ex =RT ):

:9)

(2

similarly

:10)

(2

If ex is constant then rex is zero. Then, for a stationary flux J (r ) we find that
according to equation 2.6, c(x) is a linear function of x and the gradient in equation 2.7
is equal to (c(d) , c(0))=d. Equation 2.7 now reduces to

J = ,DS dc ;

(2

S = exp(,ex=RT ):

(2

:11)

with

Equation 2.11 expresses the solution-diffusion mechanism.

:12)

2.3 Experimental measurement of permeabilities.

The simplest method to experimentally measure both the permeability coefficient P and
the diffusion coefficient D is the time-lag method. This method was first proposed
by Daynes [10] and refined by Barrer[11]. In this technique the membrane is initially
evacuated from any residual gas by applying vacuum to both sides of the membrane for
several hours. A schematic set-up of the experiment is show in fig. 2.2. Then at time
t = 0 the upstream side of the membrane is exposed to the desired gas at the desired
pressure Pfeed . From that moment on the pressure on the downstream side is measured
and plotted. A typical plot of the pressure vs. time is also shown in fig. 2.2. From the
1

Note that it is not necessary to explicitly simulate a membrane with actual interfaces. This would
place high constraints on the MD simulations. All the information needed from the simulations is the
diffusion constant D in the bulk polymer and the excess chemical potential ex of the particles in the bulk
polymer compared to the ideal gas phase.

10

Transport through polymer membranes

feed

dP

Membrane

dt

Figure 2.2: Left: Schematic representation of the set-up of a time-lag measurement.

Before the experiment the valve (a) is closed and vacuum is applied to valves (b) and (c).
Then (b) is closed and at time t = 0 valve (a) is opened and Pd is recorded. Right: A
typical time-lag plot. From the time-lag  the diffusion constant can be calculated directly
and from the slope dPd =dt the permeability coefficient can be calculated.

extrapolation of the steady-state part of the curve, the time-lag  can be obtained and the
diffusivity can be calculated with:

d2 ;
6

where d is the membrane thickness. The permeation coefficient

from the slope of the straight steady-state part directly, using:

Pfeed

Mgas d
dPd ;

Vd RT
A dt

:13)

(2

can be calculated

:14)

(2

in which Pfeed is the applied upstream pressure, Vd the downstream compartment volume, Mgas the molecular weight of the penetrant gas at density  and A the membrane
area.
The solubility coefficient S is usually calculated from the diffusion and the permeability
coefficients, using the relation P = DS . But if the permeation rate is too fast it is not
possible to determine the diffusion coefficient with the desired accuracy. Then S has to
be measured separately.

2.4 Industrial applications

11

Figure 2.3: Primary types of barrier structures. a) Monolithic, single polymer. b)

Laminate of two or more polymers. Middle high barrier layer e.g. EvOH, covered with
surface layers. These interact with the environment which could damage the middle layer.
c) Reactively formed, or coated laminate. d) Polymer filled with inorganic platelets or
higher barrier polymer lamellae to enhance the turtuosity of the path of the penetrants.

2.4 Industrial applications

The type and structure of polymer film used depends on the application on hand. One
major application is the packaging industry. In this industry there usually is a demand
for high barrier properties. For example, for the packaging of carbonated soft drinks
the package should not allow the permeation of carbon dioxide, oxygen or water. For
this purpose one normally uses poly(ethylene tetraphtalate) (PET)[12]. In the packaging
of products containing fats and oils like fried snacks and meat, protection against the
effects of oxygen and light is required.
An interesting exception to the simple barrier demands is the storage of blood platelets
[13]. Blood platelets are living cells that both consume oxygen to live and generate
carbon dioxide as a metabolic byproduct. This generation of carbon dioxide presents
a large problem, since it tends to cause undesirable changes in the pH unless the
carbon dioxide can escape. An added requirement enters because the aqueous solution
containing the platelets should not lose significant amounts of water by permeation. This
case, therefore, illustrates the need for an advanced controlled atmosphere package that
is able to allow relatively free exchange of oxygen and carbon dioxide while essentially
preventing outward permeation losses of water.
But not only the type of polymer can be adjusted to the needs, also the macroscopic
structure of the membrane can be altered. As shown in figure 2.3 one can use a variety
of barrier structures besides that of a simple film to control the exchange between the

12

Transport through polymer membranes

internal and external environment.

For example, in an application where there is a need for a barrier to oxygen an often used
polymer is ethylene-vinyl alcohol(EvOH). EvOH has a very low permeability to oxygen
in the dry state. The problem however is that it loses its barrier properties at high relative
humidities, so in those cases an interface layer is placed on the EvOH membrane such
that it is shielded from the humid environment.
Another application which has large industrial interest is the selective separation of gases
by use of membranes. In these cases there is a need for both high selectivity and high
permeability. Silicone polymers have been used as selective membranes mainly because
of the latter requirement. Even though for example the selectivity of the membranes of
(O2/CO2) is only 2.0 thus allowing only an oxygen enrichment of 30% [14], the rate
of permeation is so large that it is still usefull in certain applications. The enhancement
of the selectivity usually has a negative influence on the rate of permeation, so for every
application a new tradeoff has to be made. An interesting example of the enhancement of
the selectivity is the use of polymer films containing metal complexes. The incorporation
of cobalt-porphorine complexes in a copolymer of poly(alkyl methacrylate) produced an
increase of the selectivity (O2 /CO2 ) from 3.4 to 12.8. The complex selectively absorbs
(according to a Langmuir isotherm) and transports oxygen in the membrane [15, 16].
Another class of applications are the bio(medical) applications, for example the usage
of polymers as contact lenses. Contact lenses are classified based on their mechanical
strength and physical behavior as hard, to denote glassy polymers, or soft for
amorphous or semicrystalline polymers [17]. Important properties for polymers used as
contact lenses are surface wettability and flexure and high oxygen permeability. Silicone
films have been used as a material for the past three decades[18]. Presently the polymer
used in hard lenses is usually PMMA (polymethylmethacrylaat). Most of the present soft
contact lenses are prepared from poly(2-hydroxyethyl methacrylate) (PHEMA), but also
polypeptide films are used as contact lenses (as well as in other biomedical applications)
[19].
Controlled drug release is another biomedical application. The therapeutic efficacy of
drugs can be greatly enhanced and their toxicities reduced by delivering the drugs at
a controlled rate. Controlled release drug administration not only means prolongation
in the duration of drug delivery, but also implies predictability and reproducibility. A
number of therapeutic transdermal (through-skin) products employing silicone rubbers
(including PDMS) are commercially available. For example for the controlled release
of anesthetic vapors [20] or steroids [21].
In all these and other applications computer modeling of the permeation transport could
be of crucial importance to either a better understanding of the process or even the design
of new polymers.