PACKAGING TECHNOLOGY AND SCIENCE VOL 8 271-277 (1995)

Permeability of Naphthalene in D i f f e r e n t
types of Polymeric Food Packaging
Materials

Oi-Wah Lau" and Siu-Kay Wong

Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories,
Hong Kong

The relative permeabilities of naphthalene through different types of common

polymeric food packaging materials were determined by migration studies in a
controlled environment. The results illustrate that polyolefins, such as low
density polyethylene (LDPE), have a higher relative permeability than other
polymers, such as polyethylene terephthalate (PET) or polyvinylchloride co-
polymer (PVC). This was explained by the correlation between the permeabil-
i t y of the migrant and the glass transition temperature ( T , ) o f the different
polymers, as well as their polarity.

Keywords: Naphthalene; permeability; polymeric food packaging materials

INTRO DUCTlO N

It has been reported that naphthalene vapour present either in the packaging or in the
environment could lead to contamination of milk drinks contained in low density
polyethylene bottles.'12 Apart from polyethylene, there are other polymeric
substances employed as food packaging materials, some of which may not be per-
meable to naphthalene and hence should be more suitable for milk drinks as it is
anticipated that the extent of naphthalene contamination in milk drinks will depend
on the permeation of naphthalene through the polymer.
The first objective of this study was to assess the relative permeability of naphtha-
lene in various common polymers used as food packaging materials and hence to
recommend other polymer(s) more suitable as the packaging material for milk drinks.
The relative permeability of naphthalene through different types of polymeric food
packaging materials were determined by migration studies in a controlled environment.
The basic theory of permeation in polymers reveals that the glass transition
temperature (T,) and the polarity of the polymer are the prime parameters affecting

*Author to whom correspondence should be addressed.

CCCO894-32 14/95/050271-07 Received 23 March I995

0 1995 by John Wiley & Sons, Ltd. Revised 22 June 1995
272 0 - W . LAU AND S-K. WONG

the relative permeability of a migrant through different polymers. Hence, the second
objective of this study was to determine the correlation between the relative perme-
ability of naphthalene in various common food packaging polymers and their respec-
tive glass transition temperatures and polarities.

MATERIALS A N D METHODS

Instrumentation

The naphthalene content of each sample was determined by gas chromatography

after extraction from the sample. The analysis was accomplished with a Hewlett
Packard 5890 Series I1 chromatograph equipped with a flame ionization detector
and a HP-5 fused silica capillary column (30 mx0.53 mm i.d., 1.5 pm film thickness).
The gas chromatographic conditions used were: injector and detector temperatures
230°C and oven temperature held at 70°C for 5 min and then increased to 230°C at
6"C/min-', the final temperature being held for 5 min. Nitrogen, at a head pressure of
10p.s.i. was used as the carrier gas.

Materials and Reagents

The peanut oil used for the migation studies was purchased from a supermarket.
Naphthalene standard, tetramethylbenzene (internal standard) and all other reagents
were of analytical reagent grade.
Stock internal standard solution was prepared by dissolving 0.05 10 g tetramethyl
benzene in 50ml distilled heptane in a calibrated flask. Working internal standard
solution was prepared by diluting 0.5ml of the stock internal standard solution to
50ml with distilled heptane in a calibrated flask.
Stock standard solution (1000 pgjml-') was prepared by dissolving 0.0500 g
naphthalene in 50 ml distilled heptane in a calibrated flask. Working standard solu-
tions (2.5, 5.0 and lO.Opg/ml) were prepared by mixing 0.125, 0.25 and 0.50ml of
the stock solution, respectively, with 0.5 mi of the stock internal standard solution
and then diluting to 50ml with distilled heptane in calibrated flasks.

Procedure

The packaging materials for different food items were identified by infra-red spectro-
metry. A saturated naphthalene vapour environment was established by placing 40 g
solid naphthalene inside a sealed container (dimensions 25 x 7 x 21 cm) which was
allowed to stand for several weeks to attain an equilibrium state.
In the migration studies, peanut oil was used as the food simulant. Different types
of plastic food containers were filled with peanut oil and sealed with aluminium foil.
PERMEABILITY OF POLYMER FILMS TO NAPHTHALENE 273

The plastic containers were then left in the controlled environment for 6 days before
20g oil was taken out and placed in the 500ml round-bottomed flask of a Dean and
Stark apparatus together with 2 ml internal standard (in heptane), 180 ml saturated
NaCl solution and 1 ml anti-foaming agent (an aqueous emulsion containing 30 O h
w/w silicone). The mixture was heated to boiling over 15 min and refluxed for 2 h.
The heptane extract collected was dried over anhydrous sodium sulphate and the
naphthalene concentration in the extract was determined by gas chr~matography.~
The surface area corresponding to the 20g oil sampled was also estimated for each
type of plastic container.

THEORY OF MIGRATION IN PLASTIC

Free-volume model

A number of models for gas or organic vapour transport in polymers have been
proposed during the last 20-30 The free-volume model, based on Cohen
and Turnbull’s theory,’ suggests that diffusion results from a re-distribution of free
volume voids caused by random fluctuations in local density. This model is valid
for most penetrant/polymer systems with diffusion coefficients that exhibit strong
concentration dependence, such as organic vapours in amorphous polymers. Based
on this model, it can be predicted that a polymer having a glass transition temperature
( Tg) far below room temperature will exhibit a high frequency of motion, resulting in
a high permeability or diffusion coefficient of the diffusing molecules at room
temperature. On the other hand, a polymer having a glass transition temperature
higher than room temperature will exhibit practically null permeability at room
temperature.

Interaction between the polymer and diffusing molecules

Apart from the physical properties, such as the glass transition temperature ( Tg), the
chemical properties of the polymer will also affect the permeability of the diffusant in
it. Permeability is a composite quantity comprising the diffusion coefficient and the
solubility coefficient. From thermodynamics, a diffusant vapour will be dissolved in
a solid only if the dissolved state exhibits a lower free energy than the initial state.
If the forces between the vapour molecules and the polymer molecules are stronger
than those between adjacent polymer molecules in the solid phase, then solubility is
favoured and the solubility coefficient is high. The chemical property that governs
the strength of such inter-molecular interaction will be the polarity of the vapour,
as well as that of the polymer molecules. Thus, it would be expected that polar organic
vapours will have a larger solubility coefficient, i.e. higher permeability, in a polymer
with a larger polarity.’ In contrast non-polar vapours will have a lower permeability
in polar polymers.
274 0-W. LAU AND S-K. WONG

Table 1. The nature of polymeric material used for packaging various types of
food
Type of Polymer Type of Food

Low density polyethylene (LDPE)
High density polyethylene (HDPE)
Polypropylene (PP)
Polystyrene (PS)
Butadiene-styrene-co-polymer ( BSC)
Polystyrene foam (PSF)
Polyethylene terephthalate (PET)
Polyvinyl chloride co-polymer (PVC)
Milk drink, fruit, bread, frozen meat products,
salad dressing
Milk drink, beverage
Chinese dim-sum, candies, cake
Yoghurt, margarine, ice-cream
Cold drink, ice cream, chocolate
Fast food, cup noodle
Edible oil, soft drink, distilled water
Edible oil, soft drink

In the present study, the relative permeability of naphthalene in various polymers

having different glass transition temperatures and polarities were determined to check
whether there is any correlation between the permeability of naphthalene in different
polymers and their respective glass transition temperatures and polarities.

RESULTS AND DISCUSSION

Packaging materials for more than a hundred different food items were identified and
grouped together according to the nature of the polymers used (Table 1).
Containers of representative polymeric packaging materials were selected for the
permeability test. The determinations were made at room temperature (25OC) (Table2).
As permeability is inversely proportional to the specimen thickness, which varied
among different samples, the permeability of naphthalene in the different polymers
should be compared as the product of naphthalene permeated per unit area and
the thickness of the specimen, referred to here as the 'relative permeability'.
From Table 2 it can be seen that among the eight common food packaging poly-
mers, the polyolefins, namely LDPE, HDPE and PP, have rather high relative perme-
abilities and PET and PVC have the lowest relative premeabilities. Hence, the latter
two polymers are more suitable for use as food packaging polymers, since contamina-
tion due to naphthalene vapour or vapours from other volatile non-polar molecules
will be reduced or avoided.

Relative permeability and glass transition temperature

'
The glass transition temperature ( Tg)'Oil for each type of polymeric material are also
included in Table 2 and plotted in Figure 1. However, Tgvalues for butadiene-styrene
co-polymer (BSC) and polystyrene foam (PSF) are not available in handbooks or
reported in the literature.
PERMEABILITY OF POLYMER FILMS TO NAPHTHALENE 275

From Figure 1 it can be seen that polymers having Tg values higher than room
temperature (298K) exhibit a very low or practically null relative permeability of
naphthalene, whereas polymers having a Tg value lower than room temperature
exhibit a considerable relative permeability of naphthalene. Further, the relative
permeability decreases rapidly as the Tgvalue increases.
This observation is consistent with the previous prediction from the free-volume
model in a polymer. However, only a qualitative treatment could be considered
here as the reported Tg values are only estimated values, which vary greatly among
different grades and formulations. Moreover, it was observed that polystyrene foam
had a higher permeability than polystyrene, possibly owing to the introduction of
more air space in the foam. A similar enhancement will also be expected in plasticized
PVC co-polymer, where the flexibility of the polymer chains is much higher.

Relative permeability and polarity

In the literature, the polarity of a polymer (xp)is defined as follows

where 6 is the solubility parameter and 6 is its polar component.'2 The polarities of
some polymer types have been r e p ~ r t e d , 'and
~ the values for the polymers under

Table 2. Relative permeability (25OC) of naphthalene the glass transition tem-

perature ( T g )and polarity for different types of polymer used as food packa-
ging materials
Type of Specimen Naphthalene Relative Tgt Polarity$
polymer thickness ( t ) permeated (m) permeability" (K)
(cm) Wcm2) (Ps/cm)
LDPE 0.045 32 1.44 183 0
HDPE 0.045 22 0.99 238 0
PP 0.01 7 38 0.65 263 0
PS 0.025 0.43 0.01 368 0.1 68
BSC 0.043 3 0.13 - -
PS F 0.085 1.6 0.14 - -
PET 0.046 0.1 0.005 346 0.221
PVC 0.045 0.06 0.003 358 0.146
"Given by t x m (see text for explanation)
tTaken from references 10 and 11
STaken from reference 13
276 0-W. LAU AND S-K.WONG

1.6

1.4 - LDPE
-298 K

1.2 -
1.0 - HDPE

0.8 -

0.6 -
.PP

0.4 -
0.2 -
0 I I I ps. pf.Twc
0 100 200 300 4 00

Glass Transition Temp., Tg / O k

Figure 1. A plot of the relative permeability against glass transition temperature for some polymers used as
food packaging materials

consideration are also included in Table 2, where it can be seen that the relative
permeability of naphthalene drops rapidly to a very low value or practically null value
as the polarity of the polymer increases. This is expected from the solubility of
naphthalene vapours in polymers as naphthalene is a non-polar organic compound.
Further, the inner cohesion of the solid polymer increases with the degree of crystal-
linity, as the efficiency of molecular packing assists inter-molecular interactions. l 3
Thus, everything being equal, vapour will dissolve less easily in a crystalline polymer
than in an amorpous polymer. Unfortunately, no data are available for comparison
of the relative permeability of naphthalene in polymers with their respective degree of
crystallinity.
PERMEABILITY OF POLYMER FILMS TO NAPHTHALENE 277

CONCLUSIONS

Naphthalene contamination due to naphthalene vapour can be reduced or even

avoided if milk is packaged in other polymeric packaging materials, such as poly-
ethylene terephthalate (PET) or polyvinylchloride co-polymer (PVC), instead of
low density polyethylene (LDPE). Further, the permeability of naphthalene is high
in polymers having a comparatively low glass transition temperature ( T g ) and a
very low polarity. It is anticipated that this conclusion can be applied to other
airborne organic molecules, such as benzene, toluene, the xylenes and hexanes, which
are all used as solvents in industrial or domestic applications. With a knowledge of
these relationships, a suitable food packaging polymer for fatty foods such as a
milk drink can be chosen according to the type of contaminants present in the
environment or in the packaging material.
Acknowledgements
S.K. Wong is grateful to the Croucher Foundation for the award of a scholarship and to Mr N. S. Lee, the
Government Chemist, for his encouragement and for granting study leave.

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