Polymer Degradation and Stability 73 (2001) 69–74

www.elsevier.nl/locate/polydegstab

Examination of a low density polyethylene (LDPE) film after 15

years of service as an air and water vapour barrier
Kenneth Möller *, Thomas Gevert, Arne Holmström
Department of Chemistry and Materials Technology, SP Swedish National Testing and Research Institute,
PO Box 857, S-501 15 Borås, Sweden

Received 3 January 2001; accepted 20 January 2001

Abstract
A low density polyethylene (LDPE) film used as an air and water vapour barrier for 15 years in an exterior wooden wall con-
struction has been examined regarding ageing properties. The wall in question was part of a small house used for building material
testing purposes only. During its use, the major part of the film was firmly pressed between plywood boards made of spruce and
plasterboards. By pure chance, however, parts of the film had been hanging loose over the plasterboard into the room and thus
exposed to room temperature air as opposed to the rest of the film. Different parts of the same LDPE film had thus been exposed to
natural ageing in different environments allowing for interesting comparisons to be made. Tensile testing, size exclusion chroma-
tography (SEC), oxygen induction temperature measurements, UV and FTIR spectroscopy, and MALDI mass spectrometry have
been used to examine the differently aged parts of the LDPE film. It was found that the film contained the antioxidant b-(3,5-di-
tert-butyl-4-hydroxyphenyl)-propionic octadecyl ester (trade name Irganox 1076). Despite the fact that the part of the film found
inside the wall had lost about 75% of its initial antioxidant concentration as compared to the part exposed to the room’s environ-
ment, the latter had a substantially lower stabilising power as indicated by a considerably lower oxygen induction temperature. Most
likely,the antioxidant has been ‘‘deactivated’’ through its protective action in preventing oxidative degradation of the polymer of the
‘‘room’’ film. The loss of antioxidant in the ‘‘wall’’ film can most likely be attributed to migration and loss to the surrounding wall
construction materials. Despite substantial losses of active antioxidant for both parts of the film, through different mechanisms, both
parts have retained their tensile properties as indicated by normal values of elongation- and stress-at-break. Furthermore, the SEC
chromatograms indicate no degradation of the polymer in neither parts of the film. Accordingly, the polymer itself seems not yet to
have been affected by ageing. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: LDPE; Ageing; Polymer degradation; Antioxidant; Migration; Diffusion

1. Introduction Possible degradation mechanisms have to be identified

An approach involving comparison between accelerated
tests carried out under laboratory conditions and tests on
materials undergoing ageing under in-use conditions,
seems to be the only feasible route to reliably predict the
service lifetime of polymer materials with expected life-
times of several decades. In an international cooperation
on building materials and components [1], such a metho-
dology has been developed through successive iterative
improvements, based on feed back from field studies.
* Corresponding author. Tel.: +46-33-16-51-88; fax: +46-33-10-
33-88.
E-mail address: kenneth.moller@sp.se (K. Möller).
0141-3910/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(01)00067-2
and understood by laboratory investigations. Poly-
ethylene (PE) belongs to the most thoroughly studied
polymers; for a recent comprehensive review of Gugu-
mus, see [2]. In order to assess the durability of materials,
ageing factors of importance have to be identified under
various natural service conditions. Examination of
materials exposed to such natural ageing is the only way
to achieve this knowledge.
In this study, we have examined a low density PE
(LDPE) film used as an air and water vapour barrier in
an exterior wall construction. The wall construction and
position of the film will be described below. The film has
been in service for 15 years. During this time some
minor parts of the film had instead been exposed to air
at indoor room temperature.
70 K. Möller et al. / Polymer Degradation and Stability 73 (2001) 69–74
For more than 15 years a small dismountable wooden
house with an indoor temperature of 20 C has been in
operation at our institute for long term testing of various
types of building materials and components. It consists
of commercially prefabricated external wall elements.
External paints, roofing materials, doors, thermal insu-
lating materials, and EPDM rubber gaskets have been
successively evaluated over the years. The results on the
EPDM materials have been reported elsewhere [3–5].
From the beginning of the 1960s exterior walls of
wooden houses in Sweden depended on mineral wool
for thermal insulation. To avoid air leakage and moist-
ure build up in the mineral wool, air and water vapour
barriers are indispensable: otherwise, mould growth and
decay of wood will result. This was observed repeatedly
in the 1970s when vapour barriers made from unstabi-
lised LDPE films that had been in service for about 10
years completely disintegrated and lost their barrier
function [6].
Unfortunately, the test house was not built a priori
for testing of LDPE films. Therefore, contrary to the
other materials the origin of the LDPE film material is
unknown, even by the test house producer. As a con-
sequence, the original properties of the film are also
unknown. This situation is not unusual when the studied
materials have been naturally aged for many years.
However, as a result of the problems with the vapour
barrier films mentioned above, an industrial standard for
air and water vapour barrier LDPE films was adopted
in Sweden in 1978 [7]. The standard is based on the
work of one of the authors on accelerated ageing of PE
[8]. According to the standard, LDPE films for barrier
use should contain a stabiliser package that assures an
estimated service life of more than 50 years. This is the
type of LDPE films included in our prefabricated wall
elements. Moreover, since the only purpose and use of
the test house was long term testing of various building
materials and components, the construction workers
neglected to remove excess film folded over the inner
plasterboard in the wall construction. Instead, part of the
LDPE film was hanging loose from the inside of the wall
and in no contact with the wall. The fact that one part of
the film was hanging loose in the air while one part was
firmly pressed between the wall construction materials
was discovered by one of the authors.
We have, in previous investigations, studied diffusion of
phenolic antioxidants in LDPE [9]. We have also studied
evaporation/desorption of the same antioxidants from
LDPE films to surrounding nitrogen [10]. One of the stu-
died antioxidants was b-(3,5-di-tert-butyl-4-hydroxy-
phenyl)-propionic octadecyl ester which can be found
as, e.g. Irganox 1076. We found that Irganox 1076
easily diffuses from antioxidant containing films to
antioxidant free films in good contact with each other.
On the other hand, the evaporation rate of Irganox
1076 to surrounding air (nitrogen) was found to be very
low. Since Irganox 1076 is commonly used as an anti-
oxidant, in e.g. LDPE films, we considered it likely that
the vapour barrier contained Irganox 1076. Further-
more, the situation in the test house, with one part of the
film exposed exclusively to air and another part exposed
to a very smooth wood surface, resembled our earlier
experimental conditions. In fact, we have also previously
studied migration of Irganox 1076 from LDPE films into
wood [11] as well as into an antioxidant free LDPE film.
Durability problems caused by migration of anti-
oxidants to the surroundings have been known for some
time. Perhaps the first recognition in this respect con-
cerned insulating materials for telephone cables during
the fifties and sixties [12–13].
The LDPE film was characterized using a number of
techniques including tensile testing, FTIR and UV spec-
troscopy, differential scanning calorimetry (DSC), size
exclusion chromatography (SEC) and matrix assisted
laser desorption ionisation mass spectrometry (MALDI-
MS).
2. Experimental
2.1. Material preparation
The LDPE film was incorporated in an exterior wall
construction as shown in Fig. 1. The film was firmly
pressed between plywood boards made of spruce (abies
picea) and plasterboards, i.e. the film was in contact
with one wood and one paperboard surface. As men-
tioned above, parts of the films were hanging loose over
the plasterboard into the room, as indicated in Fig. 1.
After removal, the films were first wiped off with
paper towels in order to remove dust and other solid
particles and then carefully washed in water containing
detergents. After rinsing with pure water, the films were
washed with methanol. The film inside the wall and the
Fig. 1. Schematic drawing of the wall construction.
 K. Möller et al. / Polymer Degradation and Stability 73 (2001) 69–74
freely hanging film will here be denoted film W (wall)
and film H (hanging), respectively.
2.2. Measurements
As mentioned above, the investigation of natural
ageing of the LDPE film was not planned when the test
house was built. The origin and original properties of
the barrier film are, therefore, not known. In order to
gain as much information as possible about the film a
number of techniques were used.
Size exclusion chromatography (SEC) was utilized to
determine the average molar mass and molar mass dis-
tribution for both film W and H. SEC chromatograms
were acquired by a Waters 150CV chromatograph. The
samples were dissolved in 1,2,4-trichlorobenzene con-
taining phenolic antioxidant at 135 C during 16 h under
nitrogen before testing. The evaluation of the results
was based on a standard calibration procedure for
polyethylene using polystyrene standards [14].
The films were also examined by FTIR spectroscopy
using a Mattson Cygnus 100 spectrophotometer. IR
spectra were used for identification of the polymer and
the antioxidant. They were also used to determine the
concentration of the antioxidant. The ester band at
about 1740 cm 1 was used as a measure of the anti-
oxidant concentration. FTIR spectra were acquired
directly from the 200 mm thick LDPE films. Before
obtaining spectra the surface of the films was grinded in
order to get a rough surface. This eliminates interference
fringes, which severely affect the analysis since the con-
tribution from the antioxidant is weak.
The polyethylene band at 2019 cm 1 was removed in
a spectrum from a ‘‘pure’’ reference LDPE film by use
of the FTIR computer software. This ‘‘reduced’’ spec-
trum was then subtracted from the spectra from aged
films. The band at 2019 cm 1 was not influenced by the
subtraction and was, consequently, present in the sub-
traction spectra together with any difference between
the aged films and the reference film. The 2019 cm 1
absorbance band could thus be used as an internal
standard (see Fig. 3 below). The quotient A1740/A2019 is
a measure of the antioxidant concentration, where A1740
and A2019 are the absorbances of the antioxidant and
polyethylene, respectively.
The reference film was produced from the sample
LDPE film by cryogenic grinding the film to a powder
and a subsequent extraction of the additives from the
powder by super critical fluid extraction (SFE). An ISCO
SFE instrument composed of an SFXTM 220 extractor
and two SFXTM 1000 syringe pumps was utilized.
Supercritical carbon dioxide containing methanol as a
modifier was used as extraction medium. Methanol was
added to CO2 in order to achieve a polar extraction
medium. The extracted compounds were dissolved in
tetrahydrofuran (THF). The grinded LDPE material
71
was extracted repeatedly until all antioxidant was
removed. The reference film was then made by mould-
ing the extracted LDPE powder to 200 mm thick films.
The SFE extract was used in the identification of the
antioxidant by MALDI-MS. The MALDI instrument
was a Bruker BiflexTMIII. The 337 nm nitrogen UV
laser has an effect of 107 Wcm 2 and a pulse length of 5
ns at  1 Hz. The mass resolution in the time-of-flight
mass spectrometer is >10,000. The SFE extract was
dissolved in THF as mentioned above. Picolinic acid
(PA) was used as matrix.
The concentration of the antioxidant in the films was
determined from absorbance spectra obtained in an FTIR
spectrophotometer, as described above, and in an UV-vis-
NIR spectrophotometer (Perkin-Elmer Lambda 9)
equipped with an integrating sphere.
The use of UV spectroscopy for studying solid materi-
als, especially semi-crystalline materials like polyethylene,
is limited due to problems caused by light scattering and
reflection. If such problems can be avoided, UV-spectro-
scopy has great advantages compared to IR-spectroscopy
in quantitative analysis of additives in polyolefines owing
to higher sensitivity and lack of interference from the
polymer matrix.
One way to eliminate the negative effects of light
scattering is to use an integrating sphere attachment in
the spectrophotometer. The use of an integrating sphere
in the analysis of additives in polyethylene is discussed
in detail elsewhere [10].
An Instron 5566 tensile tester equipped with a non-
contacting Instron 2663 video extensiometer was used
to acquire data of tensile stress and elongation at break
according to ISO 527. The crosshead speed was 20 mm/
min. To avoid effects of rough handling of the films, e.g.
scratching by nails, tensile test specimens were prepared
by moulding new films from cryogenic grinded powder
of the barrier film. Before testing, samples were condi-
tioned at 23 C and 50% relative humidity for 12 h. For
each film (W and H) 10 specimens were used.
In order to obtain a measure of the relative stabilisation
level of the films, oxygen induction temperature was mea-
sured with a Mettler DSC 30 TC15-TA8000. The tem-
perature increase rate was 10 K/min from 50 to 250 C in
oxygen atmosphere.
3. Results and discussion
3.1. Characterization of the polymer
Fig. 2 shows SEC chromatograms from film W and
H. The curves more or less coincide, but film W has
slightly lower values of M
 and M
 . The uncorrected
w n


weight average molar mass Mw for film W and H was
9.28104 and 9.58104 g/mol, respectively, and the
number average M
 was 2.27104 and 2.31104 g/mol,
n
72 K. Möller et al. / Polymer Degradation and Stability 73 (2001) 69–74
respectively. These differences, however, fall well within
the accuracy limits of the SEC-analysis. Thus, no sig-
nificant difference was found between film W and H.
Most likely, the M
 and M
 values are very close to the
w n
initial values.
Furthermore, the molar mass averages and the shapes
of the SEC chromatograms are very similar to those nor-
mally found for LDPE used in this type of application 20
years ago [6].
In Fig. 3 an FTIR spectrum (a) from film W is shown
together with a reference spectrum (b) from anti-
oxidant-free LDPE. In the latter spectrum the band at
2019 cm 1 has been removed (see Subsection 2.2). The
interesting point here is the overlapping bands at 1720 and
1712 cm 1, respectively, which are found in both spectra.
These bands probably originate from a ketone used as a
chain–transfer agent in the polymerisation process and
not from oxidation of the polymer.
Fig. 8 shows elongation at break for film W and H,
respectively. The mean values for the two films are very
similar and the values are comparable to values normally
found for unaged LDPE barrier films. Since elongation
at break is, perhaps, the most sensible method for
Fig. 2. SEC chromatograms from film W and H, respectively.
Fig. 3. FTIR spectra from (a) LDPE film containing the antioxidant
(Irganox 1076), (b) antioxidant-free reference film where the band at
2019 cm 1 has been removed, and (c) the subtraction spectrum (a–b).
detecting early stages of degradation of LDPE [15], no
signs of ageing were found for the polymer itself. In
Fig. 9, the corresponding values for stress at break are
shown. No significant difference between film W and H
was observed here either.
3.2. Identification of the antioxidant
Fig. 3 shows that the barrier film contains a compo-
nent giving rise to an absorption band at 1741 cm 1,
typical for an ester group. Furthermore, in Fig. 4 the
UV spectrum from the film shows strong absorption
around 282 nm indicating the presence of an aromatic
ring. Both the FTIR and UV bands are typical for a
hindered phenol like Irganox 1076.
Fig. 5 shows a MALDI mass spectrum acquired from
the SFE extract. The peak at 531 Dalton most likely
originates from Irganox 1076 plus an added proton.
This peak is not found in extracts from LDPE which
does not contain Irganox 1076.
Most of the peaks present in the mass spectrum arise
from fragmentation of the matrix in the ionisation pro-
cess and some may originate from other low molar mass
Fig. 4. UV spectrum from an antioxidant containing film.
Fig. 5. MALDI-MS spectrum acquired from an SFE extract of the
barrier LDPE film (W).
 K. Möller et al. / Polymer Degradation and Stability 73 (2001) 69–74
compounds present in the LDPE film. It was, however,
out of the scope to identify these compounds in this
investigation.
Referring to the findings above we think that we have
positively identified the antioxidant as Irganox 1076.
3.3. Determination of antioxidant concentration in the film
Ten 22 cm samples were randomly cut out from film
W and H, respectively. UV and FTIR spectra were
obtained on the films as described above. A typical UV
spectrum from an H film is shown in Fig. 4. The peak
height at 282 nm is utilized as a measure of the anti-
oxidant concentration. In a previous study [10], we have
demonstrated that the Beer–Lambert law is obeyed in
the concentration range of interest, i.e. the correlation
between absorbance and concentration follows a
straight line, which passes through the origin. In Fig. 6,
the absorbance values for film W and H, are presented.
A drastically lower concentration of antioxidant is
observed in the wall film compared to the loosely hang-
ing film. The absorbance for film H corresponds to a
concentration of about 0.1 wt.%, which is a reasonable
value for a new and normally stabilised LDPE film. The
Fig. 6. Distributions of the results from the UV spectroscopic investi-
gation of film W and H, respectively. Mean values and standard
deviations are given in the figure.
Fig. 7. Distributions of the results from the FTIR spectroscopic
investigation of film W and H, respectively. Mean values and standard
deviations are given in the figure.
73
concentration of antioxidant in film W is only about
25% of that of film H. Since the concentration in film H
corresponds to a normal Irganox 1076 level, 75% of the
initial amount of antioxidant has disappeared from the
wall film. The only feasible explanation to this dis-
appearance is migration of the antioxidant into the sur-
rounding plywood and the paperboard surface of the
plasterboard. Fig. 7 shows the results from the FTIR
investigation. The FTIR results confirm the findings
from the UV investigation that a great portion of the
initial amount of the antioxidant has disappeared from
the wall film. This explanation is also in good agreement
with our previous findings from thermally accelerated
experiments as discussed above [9–11].
3.4. Relative stability of the film material
The results from the oxygen induction temperature
measurements, shown in Fig. 10, were really surprising
to us. We have demonstrated above a considerably
higher loss of antioxidant in the wall film compared to
in the loosely hanging film. Therefore, we expected that
the loss of antioxidant should manifest itself in a sig-
nificant decrease in induction temperature for the wall
Fig. 8. Distributions of the results from the elongation at break
investigation of film W and H, respectively. Mean values and standard
deviations are given in the figure.
Fig. 9. Distributions of the results from the stress at break investiga-
tion of film W and H, respectively. Mean values and standard devia-
tions are given in the figure.
74 K. Möller et al. / Polymer Degradation and Stability 73 (2001) 69–74
Fig. 10. Distributions of the results from the oxygen induction tem-
perature investigation of film W and H, respectively. Mean values and
standard deviations are given in the figure.
film. The result was the opposite. Fig. 10 shows that the
wall film has an induction temperature of 225 C, while
the corresponding value for the hanging film is only
211 C. Film H is thus less stabilized than film W. A
virgin LDPE film for vapour barrier purposes stabilized
with phenolic antioxidant containing systems normally
shows induction temperature around 225 C, while
additive free LDPE has an induction temperature of
about 200 C.
One explanation for the seemingly contradictory
results between the UV and FTIR investigations on the
one hand and the oxygen induction temperature investi-
gation on the other is that the active form of the anti-
oxidant in the hanging film to a great extent has been
used up while protecting the LDPE from thermo-oxida-
tive degradation. The transformation of the antioxidant
has, however, not influenced the ester bonds as mea-
sured by FTIR or the aromatic rings as measured by
UV, which is in accordance with the expected reaction
mechanism for the stabilizing action of a phenolic anti-
oxidant such as Irganox 1076 [16].
The wall film has an induction temperature equal to
that of a new film despite the fact that about 75% of the
original amount of antioxidant has migrated out of the
film. One can, therefore, not exclude that active protective
substances from the surrounding plywood and plaster-
board have migrated into the wall film.
4. Conclusions
We have examined an air and water vapour barrier
LDPE film used in an exterior wall construction, with
different parts having been exposed to different envir-
onments during 15 years. One part was exposed to the
building materials plywood and plasterboard. The other
part was exposed to indoor air at room temperature.
After 15 years of service, the LDPE film does not seem
to be affected by ageing as indicated by the normal and
reasonable levels of the values for elongation-at-break
and stress-at-break. Furthermore, molecular mass dis-
tribution curves and average molar masses have normal
shapes and values, respectively.
Nevertheless, ageing has influenced the material. The
antioxidant Irganox 1076 is severely affected. Two dif-
ferent routes were identified. Inside the wall, the anti-
oxidant had been lost by migration to the surrounding
materials. The oxygen induction temperature was, how-
ever, comparable to a virgin LDPE film. Migration of
stabilizing compounds from the surrounding materials
into the LDPE film cannot be excluded.
In the part of the film that had been exposed to air
only, no physical loss of antioxidant was observed.
However, a significant decrease in oxygen induction
temperature indicates a severe loss of active stabilizing
power. Most likely the antioxidant has been ‘‘deacti-
vated’’ through its protective action in preventing oxi-
dative degradation of the polymer. As mentioned above
the polymer itself seems not to have been affected by
ageing for 15 years.
Acknowledgements
Mr. Lars-Inge Kulin at the Department of Polymer
Technology, Chalmers University of Technology, is
acknowledged for help with the SEC measurements.
References
[1] Masters LW, Brandt E. Mater Struct 1989;22:385–92.
[2] Gugumus F. Polym Degrad Stab 1999;66:161–72.
[3] Holmström A, Eriksson K. Third International Conference on the
Durability of Building Materials and Components. Helsinki Statens
Tekniska Forskningscentral VTT Symposium 1984;49:147–64.
[4] Holmström A, Eriksson-Widblom K. International Rubber
Conference IRC 86 Gothenburg 1986;2:520–1.
[5] Holmström A. SP Rapport 1986:17 (in Swedish).
[6] Holmström A. Unpublished results.
[7] Plastic films intended for use in buildings as air- and vapour
barriers — requirements and test methods. Swedish Plastics Fed-
eration. Stockholm, SPF Verksnorm 2000, 1978.
[8] Holmström A. The course of thermooxidative degradation of
LD- and HD-polyethylene under accelerated testing conditions.
In: Eby RK, editor. Durability of macromolecular materials,
ACS symposium Series No. 95. Washington, DC: American
Chemical Society, 1979. p. 45–62.
[9] Möller K, Gevert T. J Appl Polym Sci 1994;51:895.
[10] Möller K, Gevert T. J Appl Polym Sci 1996;61:1149.
[11] Möller K, Gevert T. Proceedings of the 7th Int Conf on the
Durability of Building Materials and Components, Stockholm,
19–23 May 1996.
[12] Pusey BB, Chen M T, Roberts W L. Proceedings of the 20th
International Wire and Cable Symposium 1971, 209.
[13] Howard JB. Proceedings of the 21th International Wire and
Cable Symposium 1972. p. 329.
[14] Kulin LI, Meijerink NL, Starck P. Pure Appl Chem
1988;60(9):1403.
[15] Langlois V, Audouin L, Verdu J. Macromol Sci Pure Appl Chem
1994;A31:1389.
[16] Pospisil J. Polym Degrad Stab 1993;39:217–32 and 103–15.