Polymer Degradation and Stability 79 (2003) 385–397

www.elsevier.com/locate/polydegstab

Degradation profile of polyethylene after artificial accelerated weathering

J.V. Gulminea, P.R. Janissekb, H.M. Heisec, L. Akcelrudd,*
a
Instituto de Tecnologia para o Desenvolvimento LACTEC, Caixa Postal 19067, CEP 81531-990 Curitiba/PR, Brazil
b
Curso de Farmácia e Bioquı´mica, Universidade Tuiuti do Paraná, Rua Marcelino, Champagnat 505, CEP 80710-250 Curitiba/PR, Brazil
c
Institute of Spectrochemistry and Applied Spectroscopy at the University of Dortmund, Bunsen-Kirchhoff-Str. 11, D-44139 Dortmund, Germany
d
Universidade Federal do Paraná UFPR, Departamento de Quı´mica, Centro Politécnico da UFPR, Caixa Postal 19081, CEP 81531-990, Curitiba/PR, Brazil

Received 30 April 2002; received in revised form 14 October 2002; accepted 21 October 2002

Abstract
Elucidation of the chemical changes that take place during the aging of polyethylene sheared electrical cables, and the correlation
of these changes with physical properties need experiments with accelerated aging assays. These were carried out using the most
representative polyethylene grades found in today’s market: low density (LDPE), linear low density (LLDPE) and high density
(HDPE). The samples were exposed to UV- and xenon arc radiation using a varying exposure time and different temperature cycles.
The changes in the material structure and properties were analyzed by differential scanning calorimetry (DSC), scanning electron
microscopy (SEM), FTIR-spectroscopy, density and hardness measurements. During degradation polar groups in the polyethylene
are generated, as well as chain scission and cross-linking. As net effects of these processes respective increases in crystallinity, den-
sity and hardness and surface cracking at late stages of degradation are observed. By varying the angle of incidence in attenuated
total reflection (ATR) experiments using FTIR-spectroscopy it was possible to detect variations in composition of distinct layers
from the surface down to a depth of 1.2 mm. Deeper layers were reached by microtoming the samples in layers down to 60 mm. The
main chemical modifications were carbonyl formation of various kinds which were identified in the FTIR–ATR spectra of degraded
polyethylene samples.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Polyethylene; Degradation; FTIR–ATR

1. Introduction addressed by Gugumus [38–43]. The failures observed

Polyethylene has been widely employed as an insulat-
ing material due to its dielectric properties combined
with long durability, low cost, easy manufacture, and
good chemical resistance [1,2]. Due to its chemical
inertness, a long term resistance to the most adverse
conditions could in principle be anticipated. Eventually,
however, it became evident that, when submitted to
prolonged exposure to weathering conditions [3–7],
extruded polyethylene used in insulation of energy dis-
tribution cables was susceptible to photo [8–20], thermal
[21–37] and mechanical [38] degradation. The important
kinetic aspects of polyethylene degradation have been
* Corresponding author. Tel.: +55-41-336-7507; fax: +55-41-266-
3582.
E-mail addresses: joseane@lactec.org.br (J.V. Gulmine), janissek@
zaz.com.br (P.R. Janissek), heise@isas-dortmund.de (H.M. Heise),
akcel@onda.com.br (L. Akcelrud).
0141-3910/03/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(02)00338-5
result from the chemical modifications that take place
within the material and lead synergetically to perfor-
mance changes. The study of the aging of polyethylene
through weathering is of great importance for the
development of more resistant materials than available
in the past, and of additives that will extend the dur-
ability of such insulating polymers.
Much work has been carried out aiming at the analy-
sis of the chemical modifications generated by aging and
its consequences on the dielectric properties. Frequently
used methods rely on calorimetric, spectroscopic and
microscopic techniques, mostly in combination with
each other [5,9,11,21,22,44–54]. Among recent investi-
gations aspects of enhanced degradability of poly-
ethylene using various additives have also been studied
[9,44]. The most important modification is through
polymer oxidation, and this effect has been recently
addressed by FTIR-spectroscopy to characterize and
quantify the oxidation products, using the attenuated
386 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
total reflection (ATR) technique for surface character-
ization [9,21,44–49] or transmission spectroscopy for
specimens in the form of microtomed or pressed films
[26,55–61].
Of particular relevance is information regarding the
qualitative and quantitative aspects of the degradation
below the surface, i.e., the depth profile of degradation
products within a given sample, after having been sub-
mitted to specific aging conditions. One way to deter-
mine the degradation profile is to microtome the sample
and, thus, to have access to different depths. However,
in order to get the profile of very fine layers, with
thickness less than 10 mm for example, the use of
microtomy becomes complicated. It is very difficult to
cut smooth slices of that order. A non-invasive and non-
destructive method to approach this problem is to make
use of the full potential of the FTIR–ATR technique,
using different crystal materials and different reflection
angles for the infrared beam at the sample–crystal inter-
face. Such a procedure allows the analysis of layers up to
different depths below 2 mm. Furthermore, with the
appropriate mathematical treatment it is also possible to
isolate distinct layers for analysis, disregarding the influ-
ence of the preceding layers. A review on refined experi-
mental techniques will be given, further on.
In this paper, our contribution is dedicated to the
development of a methodology for analyzing and eval-
uating several polyethylene based materials after acceler-
ated aging. It will be useful in the future to characterize
alterations and failures in aged materials based on the
diagnostic techniques chosen by us, with a particular
emphasis on the use of infrared ATR spectroscopy.
Results that were obtained from microtomed samples at
different depths and those obtained by FTIR–ATR spec-
troscopy are combined. The following, in today’s market
most important commercial polymer grades were studied:
low density polyethylene (LDPE), linear low density
(LLDPE) and high density polyethylene (HDPE).
2. Experimental
2.1. Sample preparation
Three different grades of polyethylene samples were
obtained as pellets from OPP Polietilenos S.A. (Cama-
çari, Brazil): LDPE (code PB 681/59), LLDPE (code
LFH 0726/20 AF), and HDPE (code HF 150), all sta-
bilized for processing with Inganox 1076 (octadecyl 1-3-
(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate) from
Ciba Geigy and Weston 399 (Tris(nonyl phenyl)pho-
sphite) from General Electric. Polymer sheets were
made from pellets with dimensions of (11
11
0.1 cm),
using aluminum molds and polyester foils in a
SCHULZ press, model PHS 15 (Joinville, Brazil). The
thermo-pressing was carried out at 130, 140 and 150  C,
for LDPE, LLDPE and HDPE respectively, at cycles
with no load for 5 min, with 1.62
108 Pa for 5 min, and
with 3.25
108 Pa for another 5 min. The sheets were
allowed to cool down to ambient temperature.
Thin sample layers were cut with a microtome, model
RM2165, from LEICA (Wetzlar, Germany). The
microtoming was performed at 20  C with the samples
embedded in an inclusion gel with a metallic support
attached to the cryo-microtome.
2.2. Sample aging
Two accelerated methods that simulate different
weathering conditions were employed. For the first
method, the Weather-Ometer (WOM) equipment from
ATLAS (Chicago, USA), model CI65, was used fol-
lowing the ASTM G26/95 method, (method A) [62].
This instrument works with a xenon lamp of 6500 W,
providing an irradiance of 0.35  0.03 W/m2 (at 340 nm)
to simulate the sunlight of Florida at noon, with cycles
lasting 102 min with an incident radiation beam at 90
and a temperature of 63  5  C, a relative humidity of
60  5% and additional 18 min with a spray using de-
ionized water, a temperature of 50 5  C and a relative
humidity of 80  5%. The individual tests lasted for 25,
50, 100, 200, 400, 800 and 1600 h, respectively. The
second accelerated aging method was performed using
the Weathering Tester (QUV) equipment, model QUV
spray UV40, from QPanel Lab Products (Cleveland,
USA) following the ASTM G53-96 method, using a
fluorescent bulb UVB with 0.60 W/m2 irradiance (at 313
nm), with cycles of UV irradiation—with an incident beam
at 90 —and a temperature at 60  C lasting for 8 h and an
additional period with a spray of de-ionized water and a
temperature at 50  C lasting for 4 h. The samples were
submitted to the aging process for a duration of 12, 24, 50,
100, 200, 400 and 800 h, respectively [63].
2.3. Analytical methods
2.3.1. Determination of apparent density
The density was measured following ASTM D792-91
[64] using a SARTORIUS analytical balance (Göttin-
gen, Germany), model BP210S, and the specific acces-
sory (model YDK01) for density measurements.
Isopropanol from NUCLEAR PA. (São Paulo, Brazil)
with a purity of 99.5% and a density of 0.78336 g/cm3
at 22  C was used as a liquid medium. Four measure-
ments were carried out for each sample of the new and
aged materials, and the results were averaged.
2.3.2. Hardness
The new and aged samples were tested in a MICRO-
TEST equipment (São Paulo, Brazil), model 720b-SB,
with a Shore D Durometer (providing a weight of 5 kg
during 30 s) and a CHRONOS cronometer following
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397 387

ASTM procedure No. D2240-91 [65]. The results from

five measurements for each sample were averaged.

2.3.3. Differential scanning calorimetry (DSC)

The equipment from NETZSCH (Selb/Bavaria, Ger-
many), model STA 40S, was used to test the new and
aged polymer specimens with scans from 20 to 300  C at
a rate of 5  C/min, under a nitrogen atmosphere during
the first step and with the introduction of oxygen in a
second step (both at a flow rate of 55 ml/min).

2.3.4. Scanning electron microscopy (SEM)

The sample surfaces were coated with a layer of gold
with a thickness of 8–10 nm by sputtering using a Baltec
(Liechtenstein, Switzerland) SCD 005 equipment, and
then analysed in a Philips (Hillsboro, U.S.A.) XL 30
electron microscope using a voltage of 10 kV. Photo-
micrographs were taken with a 500-fold magnification.

2.3.5. FTIR-spectroscopy
The equipment used was a FTIR-spectrometer from
BOMEM (Quebec, Canada), model DA8. Spectra were
recorded with a resolution of 2 cm1 using Bartlet (tri-
angular) apodization; 128 interferogram scans were
averaged to give spectra from 400 to 5000 cm1 when
recorded in transmission and from 650 to 5000 cm1
when using the ATR technique. For detection a thermal
DTGS-detector (deuterated triglycine sulfate doped
with alanine in CsI windows) was used. The ATR
accessory was from Spectra-Tech (Shelton, CT, USA),
model 300 allowing a variable angle of incidence for the
reflection measurements between 30 and 60 ; crystals of
ZnSe (refractive index nZnSe=2.4 at 1000 cm1, useful
range 20,000–700 cm1, mean refractive index 2.42) and
of Germanium (refractive index nGe=4.0 at 1000 cm1,
useful range 5000–900 cm1, mean refractive index 4.0).
2.3.6. EDS—energy dispersive spectroscopy
Chemical analysis (microanalysis) in the scanning
electron microscope (SEM) was performed by measur-
ing the wavelength and intensity distribution of X-ray
signal generated by a focused electron beam on the
specimen, with the attachment of the energy dispersive
spectrometer (EDS) to the electron microscope. The
sample preparation was the same used for SEM ana-
lyses. The voltage was 20 kV, and the magnification was
200
. The scanned area was 350
470 mm. The compo-
sition was determined by using internal standards.
3. Results and discussion
3.1. Apparent density measurements
As illustrated by Fig. 1, the apparent density
increased with the time of weathering exposure. These
Fig. 1. Variation in density of different polyethylene grades versus
accelerated aging duration under WOM- (a) and QUV-weathering
conditions (b), respectively.
results can be attributed to increases in crystallinity and
at the same time to cross-linking reactions, since in both
cases the material becomes denser due to a tighter
packing, and also due to the incorporation of oxygen,
rendering the polymer heavier.
The aging within the QUV-equipment had a more
pronounced effect on density than that within the
WOM-unit, based on the same exposure time. This
result was expected, since the irradiance (radiant inci-
dent power per unit area upon a surface, usually
expressed in W/m2 or J/m2) in QUV is practically two-
fold the corresponding to WOM. The magnitude of the
irradiance takes into account the wavelength of the
incident light. In QUV the wavelength is 313 nm, of
greater energy than the 340 nm wavelength in WOM,
both located in the most deleterious radiation range for
organic compounds: 295–385 nm [66,67]. The largest
variation in density was observed in polyethylene with
low initial density and crystallinity (LDPE): from
0.9224 to 0.9427 g/cm3 for WOM and to 0.9551 g/cm3
for the QUV weathering tester, comparing non-aged
samples with those submitted to the longest exposure
times (800 h), in each chamber. It noteworthy that these
density values are comparable to those corresponding to
HDPE. In LDPE the amorphous content is higher than
LLDPE and HDPE, rendering the material more sus-
ceptible to oxidative degradation and cross-linking [9].
The two low density sample types studied showed a
similar behavior when working with the WOM-equipment,
388 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
as can be seen from the coincidental closeness of
the experimental data points in Fig. 1a. For QUV-
weathering conditions, the LDPE-material behaved simi-
larly, but showing a considerable increase in density for
the last stage of exposure (3.8% of its initial value, after
800 h). This renders the sample to be an outlier, because
through the severe cracks in the surface, as documented
by SEM (see also Fig. 5c), degradation will take place
even at larger depths. On the other hand, the maximum
increase in density observed for HDPE was around 1%
under both aging conditions, as depicted in Fig. 1.
3.2. Hardness measurements
In Fig. 2 the results from hardness measurements are
shown. The aged samples had higher values of hardness
than found for the untreated material, and classification
is always unambiguous through the relation of
measurement results: HDPE > LLDPE > LDPE. These
changes in hardness suggest that the aging process leads
to a closer packing of the material in the macroscopic
scale, resulting in harder and denser products. In the
last stages of aging investigated here, this packing can
be attributed to modifications in the amorphous regions
which are more labile to oxidation with subsequent
chain scission. The result of this are shorter molecules
with an increased mobility so that secondary crystal-
lization processes can take place. The polar groups
introduced by oxidation can also interact through
Fig. 2. Variation in hardness of different polyethylene grades versus
accelerated aging duration under WOM- (a) and QUV-weathering
conditions (b), respectively.
intermolecular dipolar forces or hydrogen bonds, and
thus can undergo further crystallization processes as
well [4,9,44,68,69].
Apart from crystallization, cross-linking reactions
also lead to increases in hardness. Altogether, these
processes result in a nearly linear increase with time,
except for QUV aged LDPE during 800 h. The hardness
was then significantly decreased, and this could be
explained in terms of micro-fissures created simulta-
neously. They would lead to a brittle, mechanically
weaker material. The processes involved in cracking are
now under investigation using nanomechanical testing,
and the results will be published soon [70].
3.3. DSC measurements
The original materials showed melting endothermic
peaks at 113, 126 and 132  C for LDPE, LLDPE and
HDPE, respectively. In Fig. 3 the calorimetric curves for
the melting region of LDPE are presented for new and
WOM-aged materials. New thermal energy absorption
peaks (shoulders) and a broadening of the endotherm
graph were observed due to degradation. These results
can be attributed to changes in crystallite sizes, mole-
cular weight differences, that are brought about by
chain breaking and secondary recrystallization . These
shoulders have been noticed before for aged poly-
ethylenes, such as LDPE [4,9,24,44], MDPE (medium
density polyethylene) [69] and HDPE [27,68].
Apart from differences in crystallinity, DSC results
allowed the evaluation of the degradation temperature
of the materials, when taken as the first derivative of the
heat flux curves in the region of temperatures higher than
160  C. The point of inflection in this region corresponds
to the temperature where degradation begins. It is
important to point out that these tests differ from the well
known OIT measurements, which is performed iso-
thermally. In our case the oxidation temperature was
determined through dynamic scans of temperature. Also
in this case each sample behaved differently: their thermal
Fig. 3. DSC thermograms for non-degraded and differently aged
LDPE material.
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397 389

stability was found in the order: HDPE > In Fig. 5b the surface features of a LDPE sample
LLDPE > LDPE. Tertiary carbon radicals are more submitted to 1600 h WOM exposure are presented.
stable than secondary and primary ones, thus requiring Cracks are seen all over the surface, showing a pre-
less activation energy to be formed. It is expected then ferential propagation of micro-cracks with further
that a larger number or ramification sites would lead to ramifications in other directions. This effect can be
a larger number of radicals, resulting in less stable related to the specific aging conditions, but also to the
materials. The formation of tertiary radicals is stimu- processing conditions such as the thermo-pressing dur-
lated during the DSC heating scan at a larger rate in ing sample preparation. Sample cutting for micro-
LDPE, resulting in lower thermal resistance when com- scopy—under the application of mechanical stress—led
pared with LLDPE and HDPE. Fig. 4a and b show that to the formation of larger cracks, perpendicular to those
the oxidation temperature decreases rapidly at the first due to aging. The QUV exposure, when applied for a
stage of degradation (from 0 to 100 h under WOM- and period of 800 h, had a more dramatic effect as seen in
from 0 to 24 h under QUV-conditions). For longer Fig. 5c. The material is highly degraded, the cracks form
exposure times, the oxidation temperature remains
almost unchanged, and the three polyethylene grades
show the same behavior in practice. After the initial
stages, the samples suffered from aging effects such as
chain scissions and cross-linking, with similar results as
observed in the DSC scans. As a consequence of this, it
can be stated that the oxidation temperature as deter-
mined in DSC analysis is not a good parameter to
characterize the long-term aging in polyethylene sam-
ples, and other methods ought to be explored [24,27,69].

3.4. Results from SEM

The photomicrograph of Fig. 5a shows that the sur-

face of new and non-degraded material is smooth,
without cracks, holes and free of any kind of defects.

Fig. 5. SEM micrograph of a non-degraded LDPE sample surface (a),

Fig. 4. Variation of the temperature of oxidation under WOM condi- for a LDPE sample surface aged under WOM conditions for 1600 h
tions (a) and under QUV conditions (b) (data were taken from the first (b), and for a LDPE sample surface aged under QUV conditions for
derivative of the DSC curves from above 160  C). 800 h (c).
390 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
a kind of mosaic pattern with no preferential propaga-
tion tendency. The importance of the wavelength of the
irradiation is again evident.
3.5. FTIR-spectroscopy
3.5.1. Attenuated total reflectance (ATR) spectroscopy
ATR-spectroscopy is a useful technique to study of
samples showing large absorptivities in the mid-infrared
spectral range. Due to the low penetration depth of the
radiation experienced with this technique mainly surface
degradation can be studied. Another and more unique
application of ATR-spectroscopy is optical depth pro-
filing by which a component concentration or gradient
in structural changes can be probed near the bulk
material surface. Only a few spectroscopic techniques
allow the molecular structure to be probed as a function
of thickness on the order of micrometers. There have
been several approaches to obtain information on the
depth profile. A review on several approaches used in
the past has been given by Urban [71].
The first investigations on surface depth profiling
were performed using the well-established reflection
theory for weakly absorbing homogeneous samples.
Penetration depth is varied by changing the reflection
angle of incidence, polarization of the infrared radiation
and/or the refractive index by employing a different
crystal material. For this, the effective thickness
approach had been proposed, making use of the ATR-
spectra as if they were recorded in transmittance. How-
ever, for non-homogeneous materials the quantitative
relations must be modified.
By taking the inhomogeneity of the sample composi-
tion into account, more refined approaches were pub-
lished. One example is the analysis of reflectance spectra
recorded from polypropylene surfaces oxidized by O2
corona discharge, reported by Carlson and Wiles [72],
who used the effective thickness equation for thin films
[73]. Hirschfeld proposed that the depth profile could be
obtained by applying a Laplace transformation to the
absorptance spectrum [74]. Several scientists advanced
the latter algorithm [75–77]. However, as Fina pointed
out, the latter approaches were valid only for vibra-
tional bands with small absorptivities [78]. Huang and
Marek [71,79] used exact optical theory in combination
with an iterative calculation. However, for all cases a
guessed profile is necessary for starting the evaluation.
Recently, two strategies were presented by Ishida and
coworkers. One method needs various ATR-spectra
recorded at different reflection angles [80], whereas in
the other the intensities at various frequencies in a given
spectrum recorded with one single angle are taken to
calculate the depth profile in three calculation steps [81].
The sample is considered to be a anisotropic medium
consisting of isotropic stratified layers, and the calcu-
lating steps include estimation of the volume-fraction
profile by linear equations of absorbance, linear least-
squares fitting of absorbance and non-linear fitting of
reflectance. The first method (multiple angle approach)
utilizes an extinction coefficent profile as a fitting para-
meter [80], whereas the second (multiple frequency
approach) utilizes the volume-fraction profile as a fitting
parameter [81].
In this context, a recent paper was published on the
accurate estimation of the mean square electric field in
infrared ATR-spectroscopy also under strongly absorb-
ing conditions, which is a necessary requisite for quan-
titative analysis without the a priori knowledge of the
optical constants of the material studied [82]. All these
approaches need rather sophisticated mathematics, so
that the simple strategy as outlined by Sack et al. [21]
was applied in this investigation.
3.5.2. Evolution of degradation with time
In Fig. 6 the main differences observed between the
spectra of the original and aged LDPE materials are
shown for samples treated under WOM and QUV con-
ditions. The differences among the infrared spectra of
the various commercial polyethylene grades was
recently published by us allowing the distinction of each
type of polymer [83]. In the ATR spectrum of the non-
degraded LDPE sample (Fig. 6a), were observed bands
in the interval between 3400 and 3200 cm1 and above
1600 cm1, which were attributed to the absorption of
the stabilizers: the bands at 3400 and 3200 cm1 corre-
sponded to the phenolic OH group of Irganox and the
band near 1600 cm1 to the C¼C to the aromatic ring
of both additives (Irganox and Weston 399).With aging
the bands in the 3400–3200 cm1 region become broader
and coalesce, and the band at 1600 cm1 gradually dis-
appears. One reason for the increased concentration of
antioxidant at the surface is its migration during the
thermo-pressing sample preparation. Transmission
spectra of thin PE foils prepared from the same pellet
material cannot provide these spectral features, because
the technique is not surface-sensitive enough. Traces of
the stabilizer compound are still observable in the spectra
of the other two samples aged under different conditions
(Fig. 6b and c). After extended weathering exposure
these absorptions are no longer noticeable.
Another aspect that deserves to be commented on is
related to the bands in the region of 1100–1300 cm1,
that are more pronounced for the samples aged in the
WOM chamber. They result from deposition of salts on
the samples surface, originating from the sprayed water
simulating rain inside of the chamber. This assumption
was confirmed by EDS analyses, discussed below.
The absorption band around 1714 cm1, which can be
assigned to the C¼O stretching vibration of a ketone
group, grows in intensity with extended aging, and at
the same time new bands begin to appear. These
absorption bands indicate that more than one oxidation
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397 391

Fig. 6. FTIR–ATR spectrum of non-degraded LDPE material (a), of aged LDPE material under QUV conditions for 200 h (b), and under WOM
conditions for 400 h (c) (measurement conditions: ZnSe crystal, reflection angle of incidence: 45 ; the latter two spectra were offset for clarity).

product is formed, as detailed in Fig. 7. These new
bands show up after 100 h of exposure in the WOM-
equipment and after 24 h under QUV-weathering con-
ditions. The irradiance differences of the two chambers
are reflected in faster aging in QUV conditions, with
carbonyl splitting beginning with only 24 h exposition.
The carbonyl bands were assigned to C¼O stretching
vibrations in aldehydes and/or esters (1733 cm1) car-
boxylic acid groups (1700 cm1) and g-lactones (1780
cm1) [9,23,44,68].The latter are seen after 200 h expo-
sure in both aging regimes.
The carbonyl index, defined as the ratio between the
integrated band absorbance of the carbonyl around
1714 cm1 and that of the PE-polymer bands (1470
cm1), characterizes the degree of oxidation for each
polyethylene sample. The results for the samples after
different weathering exposure are shown in Fig. 8. These
curves were calculated from ATR spectra, using a ZnSe

Fig. 7. FTIR–ATR spectrum of LDPE aged during 400 h under WOM conditions showing the formation of various bands that can be assigned to
stretching vibrations of various carbonyl groups formed by the polymer oxidation processes.
392 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397

that have already been mentioned, other relevant ones

are: the wavelength of the radiation, the efficiency of the
contact between sample and crystal, and the sample
area in contact with the crystal (the sample can either
fully or only partially cover the crystal) [84]. These
parameters are correlated through Eqs. (1) to (4):
l
dp ¼
1=2 ð1Þ
2n1 sin2 eff  n221

where dp penetration depth, in mm

l wavelength, in mm
n1 refractive index of the ATR crystal
n21=n2/n1 ratio of the refractive indexes of the
sample (n2) and of the crystal (n1)
eff effective angle of reflection incidence,
in degrees

The effective angle of incidence is calculated by using

Eq. (2):
 
1 sinðIRA  IRE Þ
Fig. 8. Oxidation rates for the three polyethylene grades investigated eff ¼ IRA  sin ð2Þ
n1
and characterized by the variation of the carbonyl index (for its defi-
nition, see text) versus accelerated aging duration under WOM condi-
tions (a) and under QUV conditions (b); ATR-measurement where IRA angle measured in the accessory’s scale,
conditions: ZnSe crystal, reflection angle of 45 .
in degrees
IRE angle of the crystal’s face, in degrees

crystal with a reflection angle of 45 to provide the same

depth probing. The three polymers behaved differently:
the LDPE material was most sensitive to oxidative
aging compared to the other two polymer grades. The
stability against oxidation was in the following order:
HDPE > LLDPE > LDPE. The oxidation rates at short
exposure to aging conditions within the WOM-equip-
ment are generally larger compared to the effects
observed for half exposure times under QUV-condi-
tions. It is noteworthy that the low density polyethylene
grade (LLDPE) and the HDPE-samples submitted to
WOM exposure did not show such an accentuated
increase in the carbonyl index at the last stages of aging,
specially when compared to those observed for samples
under QUV weathering conditions. This result could be
related to the competition between oxidation and cross-
linking processes, and it seems to indicate that under
WOM exposure cross-linking is favored over oxidation.
These considerations are merely speculative, since no
crosslinking density measurements were carried out.
3.5.3. ATR-measurements for the analysis of the
degradation depth profile
By changing the angle of incidence and the ATR
crystal, the depth of the infrared radiation reaching into
the sample can be varied. Apart from the parameters
The effective path length of the beam (EPL) is influ-
enced by the refractive indexes of the sample and of the
ATR crystal, the wavelength and the number of reflec-
tions (N) inside the crystal. The relationships among
these variables are:
N ¼ ðl=tÞcoteff ð3Þ
and
EPL ¼ Ndp ð4Þ
where l and t are the length and thickness of the ATR
crystal, respectively. The crystal length in particular is
defined as the distance between the centers of the
entrance and exit apertures.
Using Eqs. (1)–(4), the parameters listed in Table 1
were calculated. The values of the penetration depth
(dp) and of the effective angle (eff) were needed to ana-
lyze the spectra of the aged polyethylene samples for
different depths. By using the carbonyl index (i.e., nor-
malized absorbance values) instead of the absorbance
band area, the influence of the number of internal
reflections, changes in the contact between sample and
crystal, and the magnitude of the electrical field of the
infrared radiation at the interface sample/ATR plate
can be eliminated.
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397 393

Table 1 (the mean depths within each individual layer, as accessed

Parameters used for the calculation of the degradation profiles in aged by difference ATR spectroscopy, were taken into account
polyethylene (data are given for the wavenumber of carbonyl stretch-
for calculating the abscissa values). The difference in the
ing vibrational band at 1714 cm1.
oxidation rate, obtained by the two weathering methods,
Crystal ~ l IRA eff n1 n2 dp N EPL becomes evident from the two diagrams that show the
material (cm1) (cm) (mm) (mm) evolution of the degradation from the surface to the
Ge 1714 5.83 35 37.5 4.0 1.5 0.48 21.7 10.5 bulk of the materials with time. At the beginning, the
45 45.0 0.39 16.7 6.5 carbonyl content at layers close to the surface is evi-
55 52.5 0.33 12.8 4.25 dently higher, but with time the carbonyl content in
ZnSe 45 45.0 2.4 1.5 1.17 16.7 19.5 deeper layers increases steadily, diminishing also the
50 47.9 0.97 15.0 14.6 difference in oxidation with depth. In samples that were
55 50.85 0.84 13.6 11.4 severely deteriorated, like the ones submitted to 1600 h
60 53.8 0.76 12.2 9.2 under WOM conditions and to 800 h under QUV
IRA is the angle measured in the ATR accessory, eff the effective weathering (not shown in Fig. 10, because out of scale)
angle of incidence, n1 and n2 are the refractive indices of crystal and a difference in the oxidation product concentrations is
sample, respectively; dp is the penetration depth of the evanescent field no longer noticeable. A plateau is reached within the
of the electromagnetic infrared radiation; N is the number of reflec- possibilities of the ATR technique as applied in this
tions inside the ATR crystal under the given experimental conditions
and EPL is the effective pathlength of the beam inside the sample
investigation, that is for a depth down to 1.2 mm.
medium) To avoid this limitation and to get access to deeper
layers, microtomy was used. Films were cut con-
secutively at a depth up to 10 mm to analyze the degra-
dation at deeper layers of a sample that was submitted
By varying the angle of incidence, the depth reached by to WOM conditions for 400 h. The microfilms were
the radiation is also varied, as already pointed out. But analyzed by transmission measurements, and the results
when a larger depth is reached in an appropriate ATR were compared to those obtained by the ATR tech-
experiment, all the contributions from the preceding nique. The results are shown in Fig. 11. A satisfactory
layers are summed up, and to separate the contribution agreement was found between the two methods, since
of a chosen single layer, it is necessary to take into an exponential fitting of the points obtained by ATR
account the absorptions from the layers above. By using and microtomy could be done. This demonstrates that
a relatively simple mathematical treatment, Sack et al. FTIR–ATR spectroscopy is a specially suitable tool for
[21] developed an equation that made it possible to depth profile surface analysis, with the additional
normalize the carbonyl absorption through the use of advantage of not requiring any previous treatment of
the carbonyl index, and also to obtain the concentration the sample, and that it can be used in conjunction with
related to only one particular layer. The schematics of microtomy to reach a broad range of depths. The
this process is illustrated in Fig. 9. Several assumptions exponential behavior of the oxidation can be explained
were made that the refractive index n2 of the sample is by the dependence of oxygen diffusion inside the mat-
constant for all samples investigated and the PE con- erial [85–88].
centration can also be approximated to be constant, Another technique with the mapping of depth profiles
that is independent of sample depth and state of oxi- of oxidation products within degraded PE samples along
dation. Furthermore, an exponential function is used a cross-section cut using simple ATR-microscopic tech-
for the description of the concentration profile of the niques, based on silverhalide fiber probes, will be repor-
oxidation products. ted elsewhere [89]. Such a technique is also applicable for
The average carbonyl group concentration relative to surface micro-domain analysis of uneven samples.
each layer can be obtained from Eq. (5):
      3.5.4. EDS—energy dispersive spectroscopy
 Aic dpi Aði1Þc dpði1Þ
Ai ¼  ð5Þ The EDS surface mapping of one representative sam-
Aip dpi  dpði1Þ Aði1Þp dpi  dpði1Þ
ple (WOM, 1600 h) is presented in Fig. 12. The presence
of sodium chloride (NaCl), silicon oxide (SiO2) and
for i=2,3,... and where Aic and Aip stands for the aluminum oxide (AlO3) was detected. Silicon and alu-
absorbance of the carbonyl groups and the polymer minum oxides absorptions are seen in FTIR–ATR
vibrational bands at depth di, respectively. The index spectra in the region of 1100–1300 cm1. This is due to
(i1) refers to the preceding adjacent layer. For i=1, the incomplete purification of the sprayed water by the
the formula breaks down to A 1 =A1c/A1p. ion exchange resin of the equipment, leaving a certain
The calculations as described resulted in the data amount of salts in the water. The peak seen around 2.1
which are plotted in Fig. 10, showing the degradation keV is originated by the gold utilized to cover the sur-
profile of the samples within the first micrometer layer face of the sample.
394 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397

Fig. 9. Schematic representation of the different depths reached by the IR-radiation using different ATR measurement conditions by changing, e.g.,
the reflection angle: dp1, dp2 and dp3 are the calculated depths defining the thickness of the layers 1, 2, and 3 from the surface. The values of A1, A2
and A3 are the absorbance values corresponding to each penetration depth. The values of A 1 , A 2 and A 3 are the average carbonyl indexes for the
respective layers, as obtained by subtracting the contribution of the preceding layers.

Fig. 10. Depth profiles obtained for the oxidation products within
LDPE under WOM conditions (a) and QUV weathering (b), which
were based on the spectral evaluation of the normalized band area
around 1714 cm1 using different angles of reflection and the ATR
crystal material of ZnSe and Ge (see also Table 1).
Fig. 11. Depth profile obtained for the oxidation products within
LDPE under WOM conditions for 400 h, as analyzed by ATR spec-
troscopy and microtomy based on the evaluation of the normalized
band area around 1714 cm1.
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
Fig. 12. EDS surface spectrum of aged LDPE (WOM, 1600 h). Magnification of 200
. The peak seen around 2.1 keV is originated by the gold
utilized to cover the surface of the sample.
4. Conclusions
The accelerated aging within the three most impor-
tant, commercially available polyethylene grades was
systematically studied using artificial weathering condi-
tions as made possible with WOM and QUV equip-
ment. QUV conditions were more severe than those of
the WOM unit, since the irradiance in the latter is two-
fold more intense than in the first mentioned. The sta-
bility against aging observed for the different
polyethylene materials was found the following order:
HDPE > LLDPE > LDPE.
Increases in density and hardness with aging indicated
an increase in the polymers’ crystallinity and/or the
occurrence of cross-linking reactions. DSC scans
showed a broadening of the melting endotherm peak
and the appearance of new peaks for PE-samples
degraded by accelerated aging, which were attributed to
changes in crystallite sizes, molecular weight differences,
that are brought about by chain breaking, and second-
ary recrystallization.
At late stages of aging the polymer material
became brittle and fragile. The surface examination
by SEM revealed that for samples under WOM
exposure the cracks seemed to have a preferential
propagation, whereas for QUV the damage was
much more severe with cracks propagating in all
directions.
395
The observed morphological changes, induced by the
different accelerated aging methods, were synergetically
related to the chemical modifications observed by the
FTIR–ATR technique. The vibrations from mainly
occurring carbonyl groups were assigned in the spectra.
The variation of the ATR reflection angle allowed the
characterization of isolated layers from the surface
down to 1.2 mm, and the results agreed well with those
obtained by the spectroscopic analysis of microtomed
samples, as observed in the exponential fitting of the
combined results of both techniques.
Acknowledgements
We wish to thank COPEL (Companhia Paranaense de
Energia ) for financial support, Dr. Gabriel Pinto de
Souza and M.Sc. Marilda Munaro for the DSC-measure-
ments, Dr. Maurı́cio Pereira Cantão for the SEM- and
Dr. Carlos Mario Garcia for the XRD-measurements.
JVG thanks LACTEC for a doctoral scholarship and
LA thanks CNPq for a research grant. HMH acknow-
ledges the support given by a CNPq travel grant. The
author from ISAS (HMH) also acknowledges gratefully
the financial support given by the Ministerium für
Schule, Wissenschaft und Forschung des Landes
Nordrhein-Westfalen and by the Bundesministerium für
Bildung und Forschung, Germany.
396 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
References
[1] Nalwa HS. Handbook of low and high dielectric constant mate-
rials and their applications—materials and processing, vol. 1. San
Diego: Academic Press; 1999.
[2] Bartnikas R, Eichhorn RM. Engineering dielectrics, vol. IIA.
Philadelphia: ASTM Publications; 1983.
[3] Carrasco F, Pages P, Saurina J, Colom X. Afinidad LII 1995;
458:231–7.
[4] Hamid SH, Amin MB. J Appl Polym Sci 1995;55:1385–94.
[5] Severini F, Gallo R, Ipsale S, Nisoli E, Pardi M. Polym Degrad
Stab 1999;65:329–35.
[6] Gijsman P, Hennekens J, Janssen K. Am Chem Soc 1996:622–
35.
[7] Scoponi M, Cimmino S, Kaci M. Polymer 2000;41:7969–80.
[8] Tidjani A, Arnaud R. Polymer 1995;36(14):2841–4.
[9] Khabbaz F, Albertsson AC, Karlsson S. Polym Degrad Stab
1998;61:229–342.
[10] Pickett JE. Macromol Symp 1997;115:127–41.
[11] Horrocks AR, Mwila J, Miraftab M, Liu M, Chohan SS. Polym
Degrad Stab 1999;65:25–36.
[12] Karlsson S, Hakkarainen M, Albertsson AC. Macromolecules
1997;30:7721–8.
[13] Bauer DR. Polym Degrad Stab 1995;48:259–67.
[14] Philippart JL, Posada F, Gardette JL. Polym Degrad Stab 1995;
49:285–90.
[15] Gijsman P, Dozeman A. Polym Degrad Stab 1996;53:45–50.
[16] Gijsman P, Sampers J. Polym Degrad Stab 1997;58:55–9.
[17] Andrei C, Andrei G, Moraru M, Moise G. Polym Degrad Stab
1999;64:165–71.
[18] Tidjani A. Polym Degrad Stab 2000;68:465–9.
[19] Lau WWY, Pan JQ. Polym Degrad Stab 1998;60:459–64.
[20] Wolter KD, Tanaka J, Johnson JF. IEEE Trans Electr Insul
1982;17(3):248–52.
[21] Sack S, Wagner H, Steger E. Acta Polym 1985;36:305–10.
[22] Han SO, Lee DW, Han OH. Polym Degrad Stab 1999;63:237–43.
[23] Setnescu R, Jipa S, Osawa Z. Polym Degrad Stab 1998;60:377–
83.
[24] Budrugeac P, Segal E. J Therm Anal 1998;53:801–8.
[25] Liauw CM, Childs A, Allen NS, Edge M, Franklin KR, Collopy
DG. Polym Degrad Stab 1999;65:207–15.
[26] Allen NS, Edge M, Holdsworth D, Rahman A, Catalina F,
Fontan E, Escalona AM, Sibon FF. Polym Degrad Stab 2000;
67:57–67.
[27] Dorner G, Lang RW. Polym Degrad Stab 1998;62:431–40.
[28] Liu M, Horrocks AR, Hall ME. Polym Degrad Stab 1995;
49:151–61.
[29] Audouin L, Langlois V, Verdu J. Die Angew Makromol Chem
1995;232:1–12.
[30] Celina M, Gillen KT, Clough RL. Polym Degrad Stab 1998;
61:231–44.
[31] Ortiz RA, Salas EAR, Allen NS. Polym Degrad Stab 1998;
60:195–204.
[32] Boubakeur A, Mecheri Y, Boumerzou M. Ann Chim Sci Mater
2000;25:457–70.
[33] Corrales T, Catalina F, Peindado C, Allen NS, Fontan E. J
Photochem Photobiol A: Chem 2001;5319:1–12.
[34] Allen NS, Katami H. Polym Degrad Stab 1996;52:311–20.
[35] Sharma N, Chang LP, Chu YL, Ismail H, Ishiaku US, Ishak
ZAM. Polym Degrad Stab 2001;71:381–93.
[36] Goldberg VM, Kolesnikova NN, Paverman NG, Kavun SM,
Stott PE, Gelbin ME. Polym Degrad Stab 2001;74:371–85.
[37] Costa L, Luda MP, Trossarelli L. Polym Degrad Stab 1997;
58:41–54.
[38] Gugumus F. Polym Degrad Stab 2000;68:337–52.
[39] Gugumus F. Polym Degrad Stab 2002;76(2):329–40.
[40] Gugumus F. Polym Degrad Stab 2002;76(3):95–110.
[41] Gugumus F. Polym Degrad Stab 2002;76(3):381–91.
[42] Gugumus F. Polym Degrad Stab 2002;75:55–71.
[43] Gugumus F. Polym Degrad Stab 2002;75:131–42.
[44] Khabbaz F, Albertssson AC, Karlsson S. Polym Degrad Stab
1999;63:127–38.
[45] Lagarón JM, Pastor JM, Kip BJ. Polymer 1999;40:1629–36.
[46] Monney L, Belali R, Vebrel J, Dubois C, Chambaudet A. Polym
Degrad Stab 1998;62:353–9.
[47] Gupta G, Chiang CP. ACS Div Polym Mater 1990:667–71.
[48] Das-Gupta DK, Cooper DE. Conference Record 1988 IEEE
Int Symp Electr Insulation, Boston, 5–8 June 1988. p. 335–
338.
[49] Delor F, Barrois-Oudin N, Duteurtre X, Cardinet C, Lemaire J,
Lacoste J. Polym Degrad Stab 1998;62:395–401.
[50] Gorur RS, Bernstein BS. IEEE Trans Power Deliv 1998;13:316–
21.
[51] Gorur RS, Bernstein BS. IEEE Trans Power Deliv 1998;13:323–
9.
[52] Birtwhistle D, Blackmore P, Krivda A, Cash G, George G. IEEE
Trans Dielectr Electr Insul 1999;6:612–9.
[53] Shimizu N, Laurent C. IEEE Trans Dielectr Electr Insul 1998;
5:651–9.
[54] Costa L, Jacobson K, Brunella V, Bracco P. Polym Testing 2001;
20:649–59.
[55] Uhniat M, Kudla S. Polym Degrad Stab 2001;71:75–82.
[56] Haider N, Karlsson S. Polym Degrad Stab 1999;64:321–8.
[57] Kurtz SM, Muratoglu OK, Buchanan F, Currier B, Gsell R,
Greer K, Gualtieri G, Johnson R, Schaffner S, Sevo K, Spiegel-
berg S, Shen FW, Yau SS. Biomaterials 2001;22:1731–7.
[58] Wu Q, Qu B, Xu Y, Wu Q. Polym Degrad Stab 2000;68:97–102.
[59] McLaughlin WL, Silverman J, Al-Sheikhly M, Chappas WJ,
Zhan-Jun L, Miller A, Batsberg-Pedersen W. Radiat Phys Chem
1999;56:503–8.
[60] Ciuprina F, Teissèdre G, Filippini JC. Polymer 2001;42:7841–6.
[61] Lee AW, Santerre JP, Boynton E. Biomaterials 2000;21:851–61.
[62] Standard practice for operating light-exposure apparatus (xenon-
arc type) with and without water for exposure of nonmetallic
materials, ASTM G26-95. Annual book of ASTM standards.
Philadelphia (PA): American Society for Testing and Materials;
1995.
[63] Standard practice for operating light- and water-exposure appa-
ratus (fluorescent UV-condensation type) for exposure of non-
metallic materials, ASTM G53-96. Annual book of ASTM
standards. Philadelphia (PA): American Society for Testing and
Materials; 1996.
[64] Standard test methods for density and specific gravity (relative
density) of plastics by displacement, ASTM D792. Annual book
of ASTM standards. Philadelphia (PA): American Society for
Testing and Materials; 1991.
[65] Standard test method for rubber property—durometer hard-
ness, ASTM D2240. Annual book of ASTM standards. Phila-
delphia (PA): American Society for Testing and Materials;
1991.
[66] Kockott D. Polym Degrad Stab 1989;25:181–208.
[67] Andrady AL. Adv Polym Sci 1997;128:47–94.
[68] Valadez-Gonzalez A, Cervantes-Uc JM, Veleva L. Polym Degrad
Stab 1999;63:253–60.
[69] Dorner G, Lang RW. Polym Degrad Stab 1998;62:421–30.
[70] Tavares AC, Gulmine JV, Leni A, Lepienski CM. Polym Degrad
Stab (submitted for publication).
[71] Urban MW. Attenuated total reflectance spectroscopy of poly-
mers—theory and practice. Washington: American Chemical
Society; 1996 [Chapter 7].
[72] Carlsson DJ, Wiles DM. Can J Chem 1970;48:2397–406.
[73] Harrick NJ, Du Pré FK. Appl Optics 1966;5:1739–43.
[74] Hirschfeld T. Appl Spectrosc 1977;31:289–92.
[75] Fina LJ, Chen G. Vibr Spectrosc 1991;1:353–61.
 J.V. Gulmine et al. / Polymer Degradation and Stability 79 (2003) 385–397
[76] Shick R, Koenig JL, Ishida H. Appl Spectrosc 1993;47:1237–
44.
[77] Shick R, Koenig JL, Ishida H. Appl Spectrosc 1996;50:1082–8.
[78] Fina LJ. Appl Spectrosc Rev 1994;29:309–65.
[79] Huang J, Urban MW. Appl Spectrosc 1993;47:973–81.
[80] Ekgasit S, Ishida H. Appl Spectrosc 1997;51:461–5.
[81] Ekgasit S, Ishida H. Appl Spectrosc 1997;51:1488–95.
[82] Ekgasit S. Appl Spectrosc 1998;52:773–6.
[83] Gulmine JV, Janissek PR, Heise HM, Akcelrud L. Polym Testing
2001;21:557–63.
397
[84] Standard practices for internal reflection spectroscopy, ASTM E
573-96. Annual book of ASTM standards. West Conshohocken
(PA): American Society for Testing and Materials, 1996.
[85] Gugumus F. Polym Degrad Stab 1996;52:131–44.
[86] Gugumus F. Polym Degrad Stab 1996;52:145–57.
[87] Gijsman P, Meijers G, Vitarelli G. Polym Degrad Stab 1999;
65:433–41.
[88] Gugumus F. Polym Degrad Stab 1997;55:21–43.
[89] Gulmine JV, Janissek PR, Küpper L, Heise HM. Appl Spectrosc
[in preparation].