1 3

Permeability Properties
of Polymers

Because of their low density, polymers are relatively permeable to gases and liquids. A more in-depth knowledge of permeability is necessary when dealing with
packaging applications and with protection coatings for corrosive environments.
The material transport of gases and liquids through polymers consists of various
steps. They are:
Absorption of the diffusing material at the interface of the polymer, a process
also known as adsorption,
Diffusion of the attacking medium through the polymer, and
Delivery or secretion of the diffused material through the polymer interface, also
known as desorption.
With polymeric materials these processes can occur only if the following rules are
fulfilled:
The molecules of the permeating materials are inert,
The polymer represents a homogeneous continuum, and
The polymer has no cracks or voids that can channel the permeating material.
In practical cases, such conditions are often not present. Nevertheless, this chapter
shall start with these ideal cases, because they allow for useful estimates and
serve as learning tools for these processes.

13.1Sorption
We talk about adsorption when environmental materials are deposited on the surface of solids. Interface forces retain colliding molecules for a certain time. Possible causes include van der Waals forces in the case of physical adsorption,
chemical affinity (chemical sorption), or electrostatic forces. With polymers, we
have to take into account all of these possibilities.

538

13Permeability Properties of Polymers

A gradient in concentration of the permeating substance inside the material

results in a transport of that substance which we call molecular diffusion. The
cause of molecular diffusion is the thermal motion of molecules that permit the
foreign molecule to move along the concentration gradient using the intermolecular and intramolecular spaces. However, the possibility to migrate essentially
depends on the size of the migrating molecule.
The rate of permeation for the case shown schematically in Fig.13.1 is defined as
the mass of penetrating gas or liquid that passes through a polymer membrane per
unit time. The rate of permeation, m , can be defined using Ficks first law of diffusion as
dc
m = DA (13.1)
dx

where D is defined as the diffusion coefficient, A is the area, and the density. If
the diffusion coefficient is constant, Eq. 13.1 can be easily integrated to give
m = DA ( c1 c2 ) / L(13.2)

The equilibrium concentrations c1 and c2 can be calculated using the pressure, p,

and the sorption equilibrium parameter, S:
c = Sp(13.3)

which is often referred to as Henrys law.

m
p1, c1

x=0

Polymer

p2, c2

x=L

Figure 13.1Schematic diagram of

permeability through a film

The sorption equilibrium constant, also referred to as solubility constant, is almost

the same for all polymer materials. However, it does depend largely on the type of
gas and on the boiling temperature, Tb, or the critical temperature, Tcr, of the gas,
such as shown in Fig.13.2.

13.2Diffusion and Permeation

SO2

SO2

Solubility
0.1
H2

N2

O2

C 2H 6

CO2

CH4

CH4

CO2
Tcr

O2
N2
log S(298) = -2.1 + 0.0123 Tb

0.01
0

C 2H 6

C 2H 4

NH3

NH3

Tb

cm3/cm3

C4H10

C4H10

C 4H 6

10

100

200
Temperature, T

300

400

Figure 13.2Solubility
(cm3/cm3) of gas in natural
rubber at 25C and 1 bar as a
function of the critical and the
boiling temperatures

13.2Diffusion and Permeation

Diffusion, however, is only one part of permeation. First, the permeating substance
has to infiltrate the surface of the membrane; it has to be absorbed by the membrane. Similarly, the permeating substance has to be desorbed on the opposite side
of the membrane. Combining Eq.13.2 and 13.3 we can calculate the sorption
equilibrium using
m = DS A ( p1 p2 ) / L(13.4)

where the product of the sorption equilibrium parameter and the diffusion coefficient is defined as the permeability of a material

mL
P = DS =
A p (13.5)
Equation 13.5 does not take into account the influence of pressure on the permeability of the material and is only valid for dilute solutions. The Henry-Langmuir
model takes into account the influence of pressure and works very well for amorphous thermoplastics. It is written as
KR

P = DS 1 +
b p (13.6)
1
+

where K = c H b /S, with c H being a saturation capacity constant and b an affinity

coefficient. The constant R represents the degree of mobility, R=0 for complete

539

540

13Permeability Properties of Polymers

immobility and R=1 for total mobility. Table 13.1 [1] presents permeability of various gases at room temperature through several polymer films. In the case of multilayered films commonly used as packaging material, we can calculate the
permeation coefficient PC for the composite membrane using
1
1
=
PC LC

i =n
i =1

Li
Pi (13.7)

Table 13.1Permeability of Various Gases through Several Polymer Films

Permeability (cm3 mil/100 in2/24 h/atm)
Polymer

CO2

O2

H2O

PET

1220

510

24

OPET

PVC

4.7540

815

23

HDPE

300

100

0.5

LDPE

425

11.5

PP

450

150

0.5

EVOH

0.050.4

0.050.2

15

PVDC

0.15

0.1

Sorption, diffusion, and permeation are processes activated by heat and, as

expected, follow an Arrhenius type behavior. Thus, we can write
S = S0e Hs / RT (13.8)

D = D0e ED / RT and
and

(13.9)

P = P0e EP / RT (13.10)

where H S is the enthalpy of sorption, ED and Ep are diffusion and permeation activation energies, R is the ideal gas constant, and T is the absolute temperature. The
Arrhenius behavior of sorption, diffusion, and permeability coefficients as a function of temperature for polyethylene and methyl bromine at 600mm of Hg is shown
in Fig.13.3 [2]. Figure 13.4 [3] presents the permeability of water vapor through
several polymers as a function of temperature. It should be noted that permeability
properties drastically change once the temperature exceeds the glass transition
temperature. This is demonstrated in Table13.2 [4], which presents Arrhenius
constants for diffusion of selected polymers and CH3OH.
The diffusion activation energy ED depends on the temperature, the size of the gas
molecule dx, and the glass transition temperature of the polymer. This relationship
is well represented in Fig.13.5 [1] with the size of nitrogen molecules, dN2 as a

13.2Diffusion and Permeation

3.9
S * 1010

3.7
3.5

log scale

3.3

P * 1010

3.1
2.9
2.7
2.5

Figure 13.3Sorption, diffusion,

and permeability coefficients, as a
function of temperature for poly
ethylene and methyl bromine at
600 mm of Hg

D * 1010
2.3
2.9

3.1

3.3

3.5

3.7

3.9

103
T

10-5
Polystyrene
Vinyl chloride/
Vinyl acetate copol.

cm /(bar*s)
2

10-6
Permeability, P

Poly vinylchloride
Polyethylene
Rubberhydrochloride
10-7

Polyvinylidenechloride

10-8

3.0

3.2

10 *1/K
-3

Inverse temperature, 1/T

3.6

Figure 13.4Permeability of
water vapor as a function of
temperature through various
polymer films

541

13Permeability Properties of Polymers

9
8
7

5
4

dx

ED

dN2

542

20
3
19
18
2

10

22

11
13

24

12

5
21
4

14

23

16

15

3
2

1
0

100

17

25

20

40

26
60

80

200

20

40

60

80

20

40

60

300
Glass transition temperature, Tg

80

400

20

40

60

80

500

20

Figure 13.5Graph to determine the diffusion activation energy ED as a function of glass

transition temperature and size of the gas molecule dx, using the size of a nitrogen molecule,
dN2, as a reference.
Rubbery polymers ( ): 1 = Silicone rubber, 2 = Polybutadiene, 3 = Natural rubber,
4 = Butadiene/acrylonitrile (80/20), 5 = Butadiene/acrylonitrile (73/27), 6 = Butadiene/
acrylonitrile (68/32), 7 = Butadiene/acrylonitrile (61/39), 8 = Butyl rubber, 9 = Polyurethane
rubber, 10 = Polyvinyl acetate, 11= Polyethylene terephthalate.
Glassy polymers ( ): 12 = Polyvinyl acetate, 13 = Vinyl chloride/vinyl acetate copolymer,
14 = Polyvinyl chloride, 15 = Polymethyl methacrylate, 16 = Polystyrene, 17 = Polycarbonate.
Semi-crystalline polymers (x): 18 = High-density polyethylene, 19 = Low density polyethylene,
20 = Polymethylene oxide, 21 = Gutta percha, 22 = Polypropylene, 23 = Polychlorotrifluoro
ethylene, 24 = Polyethylene terephthalate, 25 = Polytetrafluoro ethylene, 26 = Poly(2,6-diphe
nylphenylene oxide).

reference. Table13.2 contains values of the effective cross section size of important gas molecules. Using Fig.13.5 with the values from Table13.1 and using the
equations presented in Table13.3, the diffusion coefficient, D, for several polymers
and gases can be calculated.
Table13.4 also demonstrates that permeability properties are dependent on the
degree of crystallinity. Figure13.6 presents the permeability of polyethylene films
of different densities as a function of temperature. Again, the Arrhenius relation
becomes evident.
Table 13.2Diffusion Constants Below and Above the Glass Transition Temperature
Polymer

Tg (C)

D0 (cm2/s)

ED (Kcal/mol)

T < Tg

T > Tg

T < Tg

T > Tg

Polymethylmethacrylate

90

0.37

110

12.4

21.6

Polystyrene

88

0.33

37

9.7

17.5

Polyvinyl acetate

30

0.02

300

7.6

20.5

13.2Diffusion and Permeation

Table 13.3Important Properties of Gases

Gas

Vcr

Tb

Tcr

(nm)

(cm3)

(K)

(K)

dN2/dx

He

0.255

58

4.3

5.3

0.67

H2O

0.370

56

373

647

0.97

H2

0.282

65

20

33

0.74

Ne

0.282

42

27

44.5

0.74

NH3

0.290

72.5

240

406

0.76

O2

0.347

74

90

55

0.91

Ar

0.354

75

87.5

151

0.93

CH3OH

0.363

118

338

513

0.96

Kr

0.366

92

121

209

0.96

CO

0.369

93

82

133

0.97

CH4

0.376

99.5

112

191

0.99

N2

0.380

90

77

126

1.00

CO2

0.380

94

195

304

1.00

Xe

0.405

119

164

290

1.06

SO2

0.411

122

263

431

1.08

C2H4

0.416

124

175

283

1.09

CH3Cl

0.418

143

249

416

1.10

C2H6

0.444

148

185

305

1.17

CH2Cl2

0.490

193

313

510

1.28

C3H8

0.512

200

231

370

1.34

C6H6

0.535

260

353

562

1.41

Table 13.4Equations to Compute D Using Data from Table 13.1 and Table 13.2a
Elastomers

Amorphous thermoplastics

Semi-crystalline thermoplastics

TR = 435 K and X is the degree of crystallinity.

log D =

1
1

4
2.3R T
TD

log D =

1
1

5
2.3R T
TD

ED

ED

E 1

1
log D = D
5 1 x
TD
2.3R T

543

13Permeability Properties of Polymers

10-7

cm2/(bar*s)

Permeability, P

544

10-8

= 0.932

0.938

10-9

2.8

0.954
0.96
3.0
3.2
10-3K-1
Inverse temperature, 1/T

3.6

Figure 13.6Permeation of nitrogen

through polyethylene films of various
densities

13.3Measuring S, D, and P
The permeability P of a gas through a polymer can be measured directly by determining the transport of mass through a membrane per unit time.
The sorption constant S can be measured by placing a saturated sample into an
environment that allows the sample to desorb and measure the loss of weight. As
shown in Fig.13.7, it is common to plot the ratio of concentration of absorbed substance c(t) to saturation coefficient c with respect to the root of time.
c(t)
c

ts

Figure 13.7Schematic diagram of

sorption as a function time

13.4Corrosion of Polymers and Cracking

Steady state
diffusion

Transient
diffusion

t=0

t0

Figure 13.8Schematic diagram of diffusion as

a function of time

The Diffusion coefficient is determined using sorption curves as the one shown in
Fig. 13.7. Using the slope of the curve, , we can compute the diffusion coefficient
as

D = L2a2(13.11)
16
where L is the thickness of the membrane.
Another method uses the lag time, t0, from the beginning of the permeation process until the equilibrium permeation has occurred, as shown in Fig. 13.8. Here,
the diffusion coefficient is calculated using
D=

L2
(13.12)
6t0

The most important techniques used to determine gas permeability of polymers

are the ISO 2556, DIN 53 380, and ASTM D 1434 standard tests.

13.4Corrosion of Polymers and Cracking [5]

In contrast to metallic corrosion, where electrochemical corrosion mechanisms are
dominant, several mechanisms play a role in the degradation of polymers. Attacks
may occur by physical or chemical means or by a combination of both.
Even without a chemical reaction, the purely physical effect of a surrounding
medium can adversely affect the properties of a polymer. Due to the low density of
polymers, every surrounding medium that has moveable molecules will infiltrate
or permeate the polymer. Experiments have shown that polymer samples under
high hydrostatic pressures have even been permeated by silicone oils, which are
completely inert at low pressures. The infiltration of silicone oil caused stress
cracks and embrittlement in amorphous thermoplastics in the regions of low density, such as particle boundaries, filler material interfaces, and general surface
imperfections. If we consider imperfections or particles of characteristic size L, we

545

546

13Permeability Properties of Polymers

can perform an energy balance and conclude that the critical strain, crit, at which
a crack will occur is given by [6]
crit ~

(13.13)
EL

where E represents Youngs modulus and the adhesion tension between the
individual particles. Crack formation and propagation is shown schematically in
Fig.13.9 [7]. Figure 13.101 shows an electron micrograph of a medium permeating
through the inter-spherulitic boundaries of polypropylene.

Figure 13.9Schematic diagram of crack formation and propagation during diffusion

Desorption, schematically shown in Fig. 13.11, is also undesirable for polymeric

components. Similar to soil, which cracks as it dries out too quickly, the stresses
that arise as the medium desorbs from the polymer give rise to cracks that may
lead to failure of the component. As the absorbed medium desorbs, the polymer
component shrinks according to the loss of volume. However, inner layers that
remain saturated do not shrink, leading to residual stress build-up similar to that
occurring with a cooling component with high temperature gradients. The schematic of the residual stress build-up and concentration of the absorbed medium is
shown in Fig. 13.12 [8]. The stress history at the edge and center of a desorbing
film is shown in Fig. 13.13. The stresses that arise during desorption are easily
three times larger than during absorption. The maximum stress that occurs at the
outer edge of the part can be calculated using
E
max = saturation
(13.14)
1 v
The volume change in the immediate surface of the component is caused by the
desorption process. Auxiliary agents for processing, such as coloring agents, softeners, stabilizers, and lubricants, as well as low molecular components of the
polymer, may act as desorption agents.

1Courtesy IKV Aachen.

13.4Corrosion of Polymers and Cracking

Figure 13.10Electron micro

graph of permeating medium
through the inter-spherulitic
boundaries of polypropylene

Figure 13.11Schematic
diagram of desorption from a
plate

Concentration

t0

t1

t3

t4

t5

t4

t5

Undesirable situation

Residual stress

t2

t0

t1

t2

t3

Figure 13.12Schematic concentration (C) and residual stress ( R ) as function of time inside
a plate during desorption

547

13Permeability Properties of Polymers

x = L/2

Tensile
Stress
Compressive

548

t0

t1

t1

t1 x = 0 t1

t1

log t

Figure 13.13Residual stresses

inside a plate during desorption

13.5Diffusion of Polymer Molecules and

Self-diffusion
The ability to infiltrate the surface of a host material decreases with molecular
size. Molecules of M > 5103 can hardly diffuse through a porous-free membrane.
Self-diffusion is when a molecule moves, say in the melt, during crystallization.
Also, when bonding rubber, the so-called tack is explained by the self-diffusion of
the molecules. The diffusion coefficient for self-diffusion is of the order of
T
D ~ (13.15)

where T is the temperature and the viscosity of the melt.

References
[1]

Rosato, D., and Rosato, D.V., Blow Molding Handbook, Hanser Publishers, Munich,
(2003).

[2]

Rogers, C.E., Engineering Design for Plastics, Ed. E. Baer, Chapter 9, Robert E. Krieger
Publishing Company, Huntington, (1975).

[3]

Knappe, W., VDI-Berichte, 68, 29, (1963).

[4]

Van Krevelen, D.W, Properties of Polymers, 4th ed., Elsevier, Amsterdam, (2009)

[5]

Menges, G., and Lwer, K., Metallic Corrosion: Proceedings, 8th ICMC, 2202, Mainz
(1981).

[6]

Menges, G., Kunststoffe, 63, 95, (1973).

[7]

Menges, G. and Suchanek, H., Kunststoffe, Fortschrittsberichte, Vol. 3, Hanser Publishers, Munich, (1976).

[8]

Ptz, D., Ph.D. Thesis, IKV, RWTH-Aachen, Germany, (1977).