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Water Vapor Permeability of Polypropylene

Yuka Togashi & Masanori Hara

To cite this article: Yuka Togashi & Masanori Hara (2011) Water Vapor Permeability of
Polypropylene, Fusion Science and Technology, 60:4, 1471-1474, DOI: 10.13182/FST11-A12709

To link to this article: https://doi.org/10.13182/FST11-A12709

Published online: 07 Apr 2017.

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 WATER VAPOR PERMEABILITY OF POLYPROPYLENE

Yuka Togashi*, Masanori Hara**

Hydrogen Isotope Research Center, University of Toyama: Gofuku 3190, Toyama, 930-8555, JAPAN
*: m1041209@ems.u-toyama.ac.jp , **: masahara@ctg.u-toyama.ac.jp

To understand the water vapor transport through a II. THEORETICAL BACKGROUND

polypropylene film at near ambient temperature, water
vapor permeation and sorption measurements were
carried out using tritiated water as tracer. The activation
energy and frequency factor of the permeability were
found to be 11 kJ/mol and 1.5 x 10-10 cm3(STP) cm cm-2 s-1
Pa-1, respectively. The corresponding values of the
solubility were determined to be -30 kJ/mol and 2.9 x 10-10
cm3(STP) cm-3 Pa-1. Because the permeation can be
described by a one-dimensional diffusion model, the
diffusion coefficient was evaluated from the quotient of
permeability and solubility. The activation energy of
water diffusion through polypropylene was calculated to
be 41 kJ/mol.
I. INTRODUCTION
Hydrophobic polymers are widely used for packaging
of foods and medicines in spite of the known fact that
hydrophobic polymers absorb some water and this water
may undergo permeation. Water permeation through
packaging polymers can be the cause of detrimental
The water vapor permeation through a hydrophobic
polymer film taking place under steady-state conditions
with respect to the concentration gradient of water can be
evaluated by a one-dimensional diffusion model2-4;
q=
(
D Cup,H2O − Cdown,H2O ) a ⋅t , (1)
L
where q is the amount of permeated water, D is the
diffusion constant of water in the polymer, and
Cup,H2O and Cdown,H2O denote the surface concentration of
water at the upstream side and at the downstream side of
the polymer, respectively. Equation (1) also includes the
thickness of the polymer (L) and the effective permeation
area as defined by the measurement vessel (a). Since the
surface concentration is given by the solubility of water
(S) at the prevailing water vapor pressure, Eq. (1) can be
rewritten as

( ) a ⋅t .
dampening. Polymers are also applied to prevent dermal
contact with harmful substances such as acids, bases or DS Pup,H2O − Pdown,H2O
radioactive materials. When handling tritiated water, the q= (2)
L
permeation of tritiated water through the polymer can
result in body contamination1. Assuming the water vapor pressure Pup,H2O to be constant
Studies of water sorption and permeation through
polymers are of importance to many industries. Accurate and Pdown,H 2O = 0 , the amount of permeated water
measurements of water sorption and diffusion through
becomes
hydrophobic polymers are, however, difficult to perform2.
Polypropylene is a hydrophobic polymer widely used for DSPup,H2O
packaging applications and protective purpose. In spite of q= a ⋅t . (3)
this, at least to our knowledge, the enthalpy of water L
dissolution and the activation energy of water diffusion
through this material have only scarcely been studied. The DS term in Eq. (3) is actually the permeation
In this work the water transport properties of coefficient of water through the polymer. The temperature
polypropylene have been investigated at near ambient dependence of the diffusivity (D) and of the solubility (S)
temperatures using tritiated water. is given by the following expressions

FUSION SCIENCE AND TECHNOLOGY VOL. 60 NOV. 2011 1471

Togashi and Hara WATER VAPOR PERMEABILITY OF POLYPROPYLENE

− ED 100
D = D0 e RT (4)
80

Transmittance /%T
−ΔH S
60
S = S0 e RT
(5)
40
where D0 and ED are the pre-exponential factor and the
activation energy of water diffusion, and ΔH S is the 20

enthalpy of solution. From permeability and solubility 0

4000 3500 3000 2500 2000 1500 1000 500
measurements it is possible to calculate the activation -1
Wavenumber ν / cm
energy of water diffusion through polypropylene.

Fig. 1. Infrared absorption spectrum of the sample

III. EXPERIMENTALS polypropylene film.

III.A. Permeation measurement

Thermostat

The polypropylene film used in this work was Flow

purchased from Omega data system, the Netherlands. The
supplier guaranteed a film thickness of 6 x 10-6 m. Figure
1 shows the infrared absorption spectrum of the polymer.
The absorption peaks agreed well with the reference
spectrum of polypropylene5. Since the spectrum gave the
obvious interference fringe, the thickness of the film was
uniform and it was evaluated to be 5.8 x 10 -6 m. This
value is very close to that specified by the supplier.
The apparatus for the permeation measurement is
shown in Fig. 2. Details of the apparatus have been
described elsewhere6. The apparatus consists of a stainless
steel measurement vessel, a carrier gas supply and several
water bubblers. The vessel defines the effective
permeation area of 28.3 cm2. The sample polymer film
was fixed to the vessel using Viton O-rings. The vessel
volume was about halved by the film. In the bottom
volume a cup was placed containing 10 cm3 of tritiated
water. The activity of tritiated water was determined to be
4.10 x 106 Bq ml-1 by liquid scintillation counting. This
activity corresponds to [HTO]/[H2O] = 6.88 x 10-8. To
keep the temperature constant, the vessel was placed in a
thermostat. Experiments were carried out at temperatures
within the range 278 - 313 K. The humidity in the bottom
volume was nearly 100 %. To transport the permeated
tritiated water to the bubblers, the upper volume of the
vessel was swept by argon or dry-air as carrier gas. The
dew points of both carrier gases were below 223 K. The
flow rate was maintained constant at 30 sccm during the
course of a measurement. The cumulative amount of
tritiated water in the bubbler was periodically assayed
using the liquid scintillation counting technique. The
same film was used for a series of permeation
measurements to maintain the dry surface condition of the
film at the down-stream side.
Meter
Carrier
gas
Flow Dew-point
Meter Meter
Water
Bubbler
Film
Tritiated water
4.10MBq/ml
Fig. 2. Schematic apparatus diagram of water vapor
permeation measurement.
III.B. Sorption measurements
The sorption of water by polypropylene was
measured with tritiated water. The sample film and the
glass cup filled with tritiated water were stored in the
stainless steel cell. The cell was placed in the thermostat
at several constant temperatures in the range 283 - 313 K
for a sufficient period of time. The tritium concentration
in the film was assayed by liquid scintillation counting.
IV. RESULTS
Figure 3 shows the cumulative amount of tritiated
water transported through the polypropylene film as
function of time using dry-air as carrier gas. The shape of
the profile of the first run at 298 K (denoted as 298K(1))
is a sigmoid. Because the film homogeneously absorbed
the light water from the air while the film was stored, the
water profile in the film was inappropriate to apply Eq.
(3) to the first run. On the subsequent permeation

1472 FUSION SCIENCE AND TECHNOLOGY VOL. 60 NOV. 2011

 Togashi and Hara WATER VAPOR PERMEABILITY OF POLYPROPYLENE

30 313K(5) Temperature, T / K

-1
298K(1)

cm (STP) cm cm s Pa
315 310 305 300 295 290 285 280 275
Carrier gas: Dry-Air 0.8

-1
25
-1
303K(2) 0.7

tritiated water, c/kBq ml

-2
Cumulative amount of
0.6 8
S. J. Mets
20 0.5
7
0.4 N. S. Sangaj
15
298K(4) Dry-air

3
0.3
Ar
10

-12
Permeability, P/10
0.2
5 283K(3)
278K(6)
0
0 200 400 600 800 1000 1200 1400 0.1
3
0.0032 0.0033 0.0034 0.0035 0.0036
Time, t/10 s -1 -1
Reciprocal temperature, T / K
Fig. 3. Cumulative amount of tritiated water Fig. 5. Water vapor permeability through
transported through polypropylene as a function of polypropylene.
time.

Temperature, T / K Temperature, T / K

315 310 305 300 295 290 285 280 275 㻟㻝㻡 㻟㻝㻜 㻟㻜㻡 㻟㻜㻜 㻞㻥㻡 㻞㻥㻜 㻞㻤㻡 㻞㻤㻜 㻞㻣㻡
-1
10

㻿㼛㼘㼡㼎㼕㼘㼕㼠㼥㻘㻌㻿㻛㻌㻝㻜㻙㻥㼙㼛㼘㻴㻞㻻㻌㼓㼒㼕㼘㼙㻙㻝㻌㻼㼍㻙㻝
㻝㻜
-1

Ar
Permeation rate, PR / Bq ml s

Dry-air
-1

-2
10

-3
10
0.0032 0.0033 0.0034 0.0035 0.0036 㻜㻚㻜㻜㻟㻞 㻜㻚㻜㻜㻟㻟 㻜㻚㻜㻜㻟㻠 㻜㻚㻜㻜㻟㻡 㻜㻚㻜㻜㻟㻢
-1
㻾㼑㼏㼕㼜㼞㼛㼏㼍㼘㻌㼠㼑㼙㼜㼑㼞㼍㼠㼡㼞㼑㻘㻌㼀㻙㻝㻌㻛㻌㻷㻙㻝
-1
Reciprocal temperature, T / K

Fig. 4. Permeation rate of tritiated water through Fig. 6. Water solubility into polypropylene.
polypropylene.

measurements, the cumulative amount of water of water is proportional to the reciprocal temperature and
monotonically increased with time. This indicates that the therefore follows Arrhenius equation. The activation
water permeation profiles obey Eq. (3). The slope of the energy and frequency factor of permeability were found
DSPup,H2O to be 11 kJ/mol and 1.5 x 10-10 cm3(STP) cm cm-2 s-1 Pa-1,
straight line gives the permeation rate ( a ). respectively. The permeability at 313 K is 1.5 times as
L large as that at 278 K. The temperature dependence of the
The temperature dependence of the rate is shown in Fig. 4. permeability is weaker than that of the permeation rate
The circle marked data were obtained with dry-air as (see Fig. 4). It indicates that the temperature dependence
carrier gas and the square ones with argon gas. There of the permeation rate is considerably affected by the
appears to be no difference between the two types of prevailing water vapor pressure at a given temperature.
carrier gases. Consequently, the rate of water permeation Figure 6 shows the water solubility in polypropylene
should also be independent of the co-existence of air and as function of reciprocal temperature. The ordinate was
argon. On the other hand, the rate increased with normalized by the polymer weight and the saturated water
temperature. The rate at 313 K is more than 10 times vapor pressure at a given temperature. As apparent the
higher than that at 278 K. Since the rate includes shape solubility decreased with increasing temperature. The
factors of the polymer (L and a) and water vapor pressure solubility at 313 K is 3 times smaller than that at 283 K.
( Pup,H O ), the rate was normalized to the water The enthalpy of water solution into the polypropylene was
2
estimated to be -30 kJ/mol.
permeability (DS). Figure 5 shows that the permeability

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Togashi and Hara WATER VAPOR PERMEABILITY OF POLYPROPYLENE

V. DISCUSSION of permeability was determined to be 11 kJ/mol. To

Only few quantitative data on the permeability of
water through polypropylene films from light water vapor
experiments have been reported in the literature7,8. They
are shown together with the results obtained in this work
in Fig. 5. A comparison with the data of Mets et al.8 and
Sangaj and Malshe7 indicate that they are higher by a
factor of about two than the results of this work. The
straight line provided by the data of this investigation (see
Fig .5) constitutes direct evidence that the water
permeability through polypropylene can be adequately
described by a one-dimensional diffusion model.
As already mentioned the permeability is given by
the product of the diffusion coefficient and the solubility.
EP ED
− −
P0 e RT
= D0 e RT
S0 e
Thus, the frequency factor of diffusion ( D0 ) and the
activation energy of diffusion ( ED ) can be calculated
from the experimentally determined permeability and
solubility. All pre-exponential factors and activation
energies obtained in this work are summarized in Table 1.
Table 1. Water vapor permeation, solubility, and
diffusivity parameters of polypropylene obtained in
this work.
Ep / kJ mol
-1
Permeability P0 /
3 -2 -1
cm (STP) cm cm s Pa
-1
ΔHS / kJ mol
Solubility
3 -3
S0 / cm (STP) cm Pa
ED / kJ mol
-1
Diffusion 2 -1
D0 / cm s
VI. CONCLUSIONS
The water vapor permeation behavior through
polypropylene film was studied using tritiated water as a
tracer. The amount of permeated water linearly increased
with the measurement time and the permeation rate
increased with temperature. The results constitute direct
evidence that the permeation behavior obeys a one-
dimensional diffusion model. The permeation rate
strongly depends on the water vapor pressure at a given
temperature. The temperature dependence of the
permeability was found to be weak. The activation energy
obtain the enthalpy of water solution into polypropylene,
the sorption of water was measured. The enthalpy was
found to be -30 kJ/mol.
The diffusion coefficient was obtained from the
quotient of the permeability and the solubility of water.
The activation energy of the diffusion of water was
evaluated to be 41 kJ/mol.
ACKNOWLEDGMENTS
This research was supported by the Ministry of
Education, Science, Sports and Culture, Grant-in-Aid for
Science research on Priority Area, KAKENHI 19055009.
ΔH S
−
RT
(6)
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