Materials Science and Engineering A 527 (2010) 1649–1654

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Study of UV-aging of thermoplastic polyurethane material

A. Boubakri, N. Guermazi ∗ , K. Elleuch, H.F. Ayedi
Unité de Recherche de Chimie Industrielle et Matériaux, URCIM – ENIS, Route de Soukra km 3.5, B.P. 1173-3038, Sfax, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, the characteristics of thermoplastic polyurethane (TPU) material exposed to artifi-
Received 15 June 2009 cial weathering environment for different durations were studied. The influence on (i) appearance and
Received in revised form 20 October 2009 morphology, (ii) thermal properties and (iii) mechanical properties evolution of the material were inves-
Accepted 6 January 2010
tigated during aging. For this purpose, ultraviolet (UV) chamber was used as accelerated aging technique.
Optical and scanning electron microscopy (SEM) observations revealed changes in appearance and mor-
phology of TPU material after UV-exposure. From differential scanning calorimetry (DSC) analysis, it was
Keywords:
mainly found that thermal properties, in terms of glass transition temperature (Tg ), were affected. Changes
UV-aging
Thermoplastic polyurethane
in mechanical behaviour were equally discerned using both computer-controlled tensile testing and abra-
Mechanical properties sive wear tester. The mechanical properties in bulk of the studied material displayed tow steps. The elastic
Thermal properties modulus and the stress at 200% of strain initially decreased and then increased progressively revealing an
increase in crosslink density. The tribological properties, in terms of wear resistance, were affected and
this degradation became more important with UV-exposure. Furthermore, our experimental results dis-
played prominently that there was a competition between chain scission and crosslinking mechanisms.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Since their appearance, polymers have been extensively used
in many fields. Some of their applications have required a deep
knowledge of the durability and predictability of the properties
under different environmental conditions and over long periods
to cover the whole lifetime of the material [1]. Thus, it is critical,
for certain applications, to find relationships between some envi-
ronmental parameters with the mechanical, physical and chemical
properties of the polymer. Natural conditions, external factors such
as sunlight rays and weather variations (temperature, humidity)
are important and difficult to control and/or to record.
It is well known that exposure of polymer materials to an
aggressive environments (i.e. UV radiation, thermal exposure,
oxidative atmosphere) causes changes in their physical, chemi-
cal, and mechanical characteristics [2–7]. In these works, changes
in calorimetric behaviour, infrared absorption bands and mechan-
ical properties were addressed. Recently, many authors [8–10]
have shown that most polymers absorb solar UV radiation, which
causes degradation due to photo and thermo-oxidative reactions.
In particular, the thermoplastic polyurethane (TPU) material is sus-
ceptible to this degradation [5,6,11]. The later is most used in a
variety of conditions such as weather exposure and aggressive ele-
ments (sunlight, UV-exposure) which can affect its durability. On
∗ Corresponding author. Tel.: +216 99 614 199; fax: +216 74 275 595.
E-mail address: noamen.guermazi@gmail.com (N. Guermazi).
the other hand, the mechanisms of such degradation are quite
complex and are usually dependent on the testing configuration
[12]. This generally requires extensive experimental characteri-
zation [13]. In fact, natural weathering tests are commonly used
to evaluate the weather resisting property of materials, but they
are time-consuming and they have bad reproducibility. However,
artificial aging procedures are generally adopted to simulate natu-
ral weathering conditions. In this context, accelerated aging tests
are examples of useful instruments to investigate the material
behaviour after environmental aging [7,14–16]. As reported in the
literature [17,18], xenon lamp, carbon-arc lamp, mercury vapour
lamps and ultraviolet fluorescent lamp are commonly used, in arti-
ficial weathering devices, as light sources to simulate ultraviolet
radiation from sunshine.
From the results reported in the literature of the UV-aging of
polymers, many important matters were discussed. The influence
of the aging process on the polymer lifetime has got a great interest
in the last few decades [19–21]. Similarly, many recent studies have
reported that UV-aging can generally provoke changes in physi-
cal properties [22,23] like cracking (microcracks) [24,25] or voids
[17] and mechanical properties [7,23,26,27]. All these modifica-
tions are a consequence of a chemical evolution of the material
when exposed to aging. In this context, two phenomena can take
place: chain scission or branching and crosslinking which are con-
currently influenced by oxygen and temperature. Claude et al. [22]
have correlated the formation of a crosslinked structure to the
increase of the glass transition temperature (Tg ) and the Young’s
modulus. Zhao et al. [17] have shown that the UV-aging induces

0921-5093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.01.014
1650 A. Boubakri et al. / Materials Science and Engineering A 527 (2010) 1649–1654

a change in their appearance, morphology, mechanical proper-

ties and their chemical structures. In particular, Rosu et al. [11]
have shown that UV-exposure of the PU modifies physical and
chemical characteristics of PU surface and results in rapid colour
change and degradation. Andersson et al. [28], with the help of
thermal and structural analysis methods, have shown that UV-
aging leads to dramatic modifications in structural and thermal
properties. Scaffaro et al. [4] have focused on the structural and
mechanical responses of polymer under the combined effects of
photo-oxidation and thermal degradation. They have shown a
change in the morphology and in the chemical structure of the
aged material, with consequent alteration of the mechanical per-
formance over time.
In terms of the material surface properties, many studies have
been conducted to understand the effect of UV-aging process on
wear resistance and also to assess surface degradation of aged poly-
mers [16,29,30]. Toohey et al. [16] have concluded that the wear
resistance strongly depends on the amount of oxidation and the
degree of crosslinking. Menzel and Blanchet [29] have shown an Fig. 1. Dimensions of the tensile test samples (in mm).
improvement of the wear resistance of certain polymeric materi-
als after aging exposure. To the author’s knowledge, the literature
dealing with the study of the effect of UV-aging on wear resistance characterized by wavelength irradiation and power of 3 mW cm−2
of TPU is not voluminous; therefore, this matter is investigated in at 340 nm and 125 W, respectively. The sample-to-lamp distance
this paper. was 20 cm. During the aging experiments, the temperature testing
The present work is aimed to examine the aging behaviour of chamber ranged from 65 to 70 ◦ C. The retained exposure durations
TPU in an artificial weathering environment produced by UV cham- were 3, 6, 12, 72 and 144 h.
ber as weathering equipment. In this regard, several techniques
were used to investigate the impact of UV-aging on the character- 2.2.2. Differential scanning calorimetry (DSC)
istics of the studied material. Changes in appearance, morphology, Thermal properties of TPU were measured using a differen-
thermal and mechanical properties of TPU before and after UV- tial scanning calorimetry machine (DSC NETZSCH instrument). The
exposure were monitored by scanning electron microscopy (SEM), retained range of temperature was [−100 ◦ C, +50 ◦ C] with scanning
differential scanning calorimetry (DSC), computer-controlled uni- rate of 3 ◦ C min−1 under a nitrogen flow. In order to obtain repro-
versal tensile machine and abrasive wear testing. ducible results, a weight of 3 ± 0.2 mg was retained for each sample.
The glass transition temperature (Tg ) was determined as the inter-
2. Material and methods section of the base line with the tangent at the inflexion point of
the heat capacity curve.
2.1. Material
2.2.3. Tensile test
The material used in this study was a polycaprolactone The tensile test was used to study the influence of UV-aging
copolyester based on thermoplastic polyurethane (translucent and on the mechanical properties of TPU. Tensile tests were performed
colourless pellets) delivered by the society MERQUINSA, in Ger- using an LLOYD instrument machine equipped with a measuring
many (reference D11T92EM). Table 1 lists some properties of the load cell. Samples, in the form of halters type 1A, were tested
used material. TPU samples were obtained by injection molding according to the NF ISO 527-2 standard at room temperature (23 ◦ C)
process in accordance with the ISO standard 527-2 type 1A (Fig. 1). and under a crosshead speed of about 10 mm min−1 . The shape of
Before injection, the PU pellets were dried for 2 h at 110 ◦ C. Molding sample with dimensions in mm is given in Fig. 1. The presented
conditions are summarized in Table 2. results were the average of three measurements for each sample.

2.2. Testing methods 2.2.4. Abrasion test

2.2.1. UV-aging test
Artificial aging undergone by samples was carried out in an
accelerated aging chamber. This type of testing chamber uses
UV radiation simulating the terrestrial sunshine. The UV lamp is
Abrasion tests were carried out on a pin-on-disc machine (Fig. 2).
Parallelipedic samples with dimensions of 10 mm × 10 mm × 4 mm
were used. Tests were carried out at room temperature under a
lubricated condition using tape water in order to avoid tear of abra-
sive paper. The samples holder was fixed on a disc attached to an

Table 1
Principal properties of the studied TPU.

Density 1200 kg m−3 Hardness 90 Shore A

Withdrawal with the molding 0.2% Stress at 100% of strain ≥12 MPa
Minimum temperature service −30 ◦ C Breaking strength ≥40 MPa
Maximum temperature service 110 ◦ C Breaking Strain ≥430%

Table 2
TPU molding conditions.

Tube machine temperature Mold temperature Injection time Injection pressure Cooling time
◦ ◦
210 C 35 C 3s 8.625 MPa 30 s
 A. Boubakri et al. / Materials Science and Engineering A 527 (2010) 1649–1654
Fig. 2. Schematic illustration of the pin-on-disc machine.
Table 3
Experimental conditions for the abrasive wear tests.
Load (N) 5 causes yellowing phenomena. In fact, irradiation modifies physi-
Rotation speed of disc (m s−1 ) 0.36
Testing time (min) 1–5
Water lubricant (mL min−1 ) 500
Abrasive paper Grade 240
electric motor. They were brought into contact with abrasive grit
SiC paper under a constant normal load. All the experimental con-
ditions for the abrasive wear tests were summarized in Table 3.
It is to be noticed that under such conditions, preliminary wear
experiments have shown that the worn of abrasive paper is not
significant.
Therefore, to obtain reproducible results, a new grit SiC paper
was used for every sample during each test. Measurement of wear
rates was taken versus the test duration. Samples were dried care-
fully and weighed. A Mettler microbalance with an accuracy of
0.1 mg was used for weighting the samples. Each value represents
the average of three tests.
Fig. 3. Colour modifications of UV-aged TPU versus exposure time: (a) unaged, (b) 6 h and (c) 72 h.
1651
3. Results and discussion
3.1. Discolouration due to UV-exposure
In order to determine whether the UV-exposure has an effect
on the appearance of the tested material, an optical microscopy
photographs were realized on the exposed surfaces during the
exposure time. Fig. 3 shows the colour variation against UV-
exposure time of unaged and aged samples. As it can be observed,
a change of the samples colour from colourless to yellow (6 h) and
then to brown (72 h) was noticed during UV-aging. In fact, the
colour density of the tested samples increases gradually with the
exposure time. This colour shifting can be ascribed to oxidation
reactions which lead to the formation of an oxidized layer on the
polymer surface. These observations are in good agreement with
those found in the literature [5,11,17,25]. Rek and Bravar [5] have
shown the formation of an oxidized structure for aged polyurethane
following UV irradiation. Recently, Rosu et al. [11] have shown
that the oxidation reaction in the backbone of the polyurethane
cal and chemical characteristics of PU surface and results in rapid
colour change and degradation. Woo et al. [25] have shown that
UV-exposure darkens the colour of certain composites. Zhao et al.
[17], when studying the UV-aging of certain polymer, have shown
that the surface of the studied material became redder, yellower
and lighter in the first stage of aging and then remained almost
unchanged.
3.2. DSC analysis
Results of the thermal analysis performed on the UV-aged TPU
were reported in Table 4. As it can be seen the glass transition
temperature (Tg ) of the aged samples varies as follows:
(i) during the first hours of exposure (after 6 h), Tg of the tested
sample was decreased compared to the unaged one (from −2.3
to −8.3 ◦ C). This fact can be attributed to the increase of the
1652 A. Boubakri et al. / Materials Science and Engineering A 527 (2010) 1649–1654
Table 4
Variation of glass transition temperature of TPU
exposed to UV-aging.
Sample Tg (◦ C)
Unaged TPU −2.3
Aged TPU 6 h UV −8.3
Aged TPU 72 h UV 5
molecular mobility. This flexibility perhaps was due to the chain
scissions caused by oxidation reactions [31]. Indeed, the UV
light induces the rupture of the link of groups attached to the
macromolecule [32]. So, it seems that the chain scission result-
ing from the oxidation reactions preferentially was occured, at
short times, in the amorphous region due to the higher per-
meability to UV radiation of this phase with respect to the
crystalline one.
(ii) the Tg of the sample exposed to 72 h increased compared
to sample exposed only to 6 h. This can be ascribed to
molecular recombination or crosslinking mechanism after this
UV-exposure duration. In fact, as aging proceeds (longer irradi-
ation times), oxidation of the polyurethane takes place. This
oxidative degradation led to the formation of a crosslinked
structure on the exposed surface. In earlier studies [33,34], it
has been reported that UV-aging involves additional crosslink-
ing to give a more highly ordered structure. Recently, Claude
et al. [22] and Tey et al. [35] have found the same findings:
Tg increases with increasing exposure time. They have inter-
preted these changes by a significant decrease of the molecular
mobility.
Finally, it is to mention that Tg was just determined for samples
exposed to UV-aging for short and long time in order to ensure
significant difference in the molecular structure.
3.3. Mechanical properties
In order to study the effect of UV-aging on the mechanical
properties of TPU, tensile tests were conducted. Figs. 4 and 5,
respectively, display the stress at 200% strain and the Young’s mod-
ulus recorded for aged samples under various radiation times. As it
can be seen, two domains were distinguished:
(i) at short time of UV-exposure (until 6 h), the mechanical prop-
erties were dramatically affected. The elastic modulus and the
stress at 200% of strain were decreased, respectively, from 39 to
34 MPa and from 12.6 to 8.8 MPa after only 6 h of UV-exposure.
According to the literature [9,14,23,27,31], the observed facts
can be ascribed to the physical degradation of the polymer
Fig. 4. Variation of stress at 200% strain versus UV-exposure time.
Fig. 5. Variation of elastic modulus versus UV-exposure time.
(oxidation, chains scissions, etc.). Tidjani [31] has reported
that changes of mechanical properties during UV-exposure
were essentially caused by chain scission reactions. The same
results were found by Oprea and Oprea [23] when studying the
mechanical behaviour of polyurethane elastomers during dif-
ferent weathering tests. They have found that the elongation,
the elastic modulus and the ultimate tensile strength decreased
with the increase of the weathering time.
(ii) after 6 h of UV-exposure, moderate increase of the mechan-
ical properties was noticed. It seems that UV-aging at long
duration involves additional crosslinking to give a more highly
ordered structure. This crosslinking was accompanied by an
increase of stability which can enhance the material strength.
The obtained results are in good agreement with those reported
in several papers [22,34,36–38]. Subocz et al. [34] have shown
that the long-term action of UV mainly consisted of addi-
tional crosslinking to form new supramolecular structures with
higher ordering. In the same context, Claude et al. [22] have
recently concluded that the formation of a crosslinked struc-
ture can be considered to explain the increase of the Young’s
modulus of the UV-exposed polymer.
Finally, the results from the mechanical characterization were
correlated to thermal analysis previously presented and these find-
ings are in good agreement with those found by Ludwick et al. [6]
when studying the UV-aging of PU.
3.4. Tribological properties
In order to study the effect of UV-aging on the tribological
properties of TPU, abrasion tests were carried out. Fig. 6(a) shows
relationships of the wear rate with the UV-exposure time at var-
ious abrasion times. As can be observed, curves present similar
tendencies with two linear parts. A first linear part allows us to
determine the slopes of wear rate versus exposure time. It was
deducted that the slope of wear rate versus time after 3 min of
abrasion becomes steeper comparatively with slopes after 1 min
(Fig. 6(b)). So, at short abrasion time (1 min), no significant differ-
ence of wear kinetics between the aged samples was perceived. This
fact can be attributed to the UV effect on surface samples. After
3 min of abrasion, there was a difference on wear rate. It can be
explained by the difference on the affected thickness layer at differ-
ent durations. Concerning the second linear parts, a light deviation
after approximately 6 h of UV-exposure occurs. Accordingly, the
TPU abrasion resistance variation was not significant.
It can be concluded that UV-exposure accentuates the wear rate.
In fact, a critical value of UV-exposure duration (6 h) was noticed.
For the first hours of exposure, the TPU experienced severe degra-
 A. Boubakri et al. / Materials Science and Engineering A 527 (2010) 1649–1654
Fig. 6. (a) Wear rate (%) of UV-aged TPU against exposure time after 1, 3, and 5 min
of abrasion time. (b) Zoom on the first linear part.
Fig. 7. Surface morphologies of unaged (a) and UV-aged TPU after sliding for 6 h (b) and 72 h (c).
1653
dation corresponding to the structural modifications [31]. Then the
TPU becomes less sensitive to the UV radiations which let us con-
cluding that UV-aging concerns especially the surface properties
[16,29,35].
3.5. Morphology of the UV-aged TPU
In order to confirm the mechanical degradation of the aged sam-
ples, the morphology of the exposed surface, after tensile tests, was
investigated using scanning electron microscopy. Fig. 7 shows the
surface morphologies of unaged and UV-aged TPU for various dura-
tions (6 and 72 h). It was noticed that microcracks start to appear
only on the exposed face of samples. Deterioration of the surface
becomes more visible as the time of radiation increases. The micro-
cracks, increase in number, propagate deeper into the material
and become broadened in width with further UV-exposure [24].
Similar microcracking phenomenon has been reported previously
[39,40] upon UV-exposure. In these works, molecular chain scis-
sions were found to occur on the polymer surface and to generate
polymer radicals. Fragments may link to the main chain of a neigh-
boring molecule to give a branched one with a higher molecular
weight. The excessive embrittlement, resulting from the genera-
tion of these crosslinked molecules, seems to be mainly responsible
for the formation of microcracks. This result is in good accordance
with those found by Woo et al. [25] when studying the UV-aging
of certain composites. These authors have shown that microcracks
started to appear on the material surface after about 300 h under
UV-exposure.
4. Conclusion
In order to investigate the UV-aging characteristics of TPU, sam-
ples were subjected to UV irradiation at ambient temperature and
in air up to 140 h.
The main objective was to determine the effects of accelerated
UV-aging radiations on the physical and mechanical properties of
TPU material. Changes in mechanical properties, material structure,
appearance and morphology were studied by using tensile test-
1654 A. Boubakri et al. / Materials Science and Engineering A 527 (2010) 1649–1654
ing, abrasive wear tester, differential scanning calorimetry (DSC)
and scanning electron microscopy (SEM). TPU material, which ini-
tially has a colourless appearance, yellower in the first stage of
aging (after 6 h), and then turn to brown (after 72 h) and there-
fore remained almost unchanged. SEM photographs have shown
the formation of microcracks on UV-exposed surfaces, especially at
long exposure duration. From DSC analysis, the thermal properties
of the studied TPU were affected. The glass transition temper-
ature (Tg ) decreased in the beginning and then increased with
UV-exposure time. Similarly, the mechanical properties, elastic
modulus and stress at 200% of strain, initially decreased and then
increased progressively revealing an increase in crosslink density.
On the other hand, the wear resistance of the material surface
decreased and this degradation became more important with UV-
exposure time. Finally, a competition between chain scission and
crosslinking mechanisms was discerned in this study.
In any further research on the UV-aging of TPU, following the
crosslink density and more thermal characterizations (melting
temperature, degree of crystallinity) appear to be of prime impor-
tance to provide more additional data.
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