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Novel dyed ethylene-norbornene composites


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Article in Polymer Degradation and Stability December 2015


DOI: 10.1016/j.polymdegradstab.2015.11.013

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Polymer Degradation and Stability 123 (2016) 137e145

Contents lists available at ScienceDirect

Polymer Degradation and Stability


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

Novel dyed ethylene-norbornene composites with enhanced aging


resistance
Anna Marzec a, *, Ewa Chrzescijanska b, Zygmunt Boruszczak a, Marian Zaborski a,
Anna Laskowska a, Gisele Boiteux c, Olivier Gain c
a
Technical University of Lodz, Institute of Polymer and Dye Technology, ul Stefanowskiego 12/16, Lodz, 90-924, Poland
b
Technical University of Lodz, Institute of General and Ecological Chemistry, ul Zeromskiego 116, Lodz, 90-924, Poland
c
University of Lyon, Universit
e Claude Bernard Lyon1, Ing
enierie des Mat
eriaux Polym eres, UMR CNRS 5223, 15 Bd A. Latarjet, Villeurbanne, 69622, France

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

Article history: The current research investigated the effects of anthraquinone solvent dyes and commercial stabilizers
Received 18 May 2015 on the aging resistance properties of ethylene-norbornene (EN) composites subjected the aging in the
Received in revised form full solar-spectrum for various time periods. During irradiation, the mechanical properties were
3 November 2015
measured by low and high degrees of deformation using dynamic mechanical analysis (DMA) and tensile
Accepted 16 November 2015
Available online 2 December 2015
tests until break, respectively. Changes in the color and surface defects in the investigated composites
were evaluated using spectrophotometry and scanning electron microscopy (SEM). An accelerated aging
test revealed that the application of solvent dyes with anthraquinone chromophores signicantly pro-
Keywords:
Anthraquinone solvent dye
longed the lifetimes of the EN composites during aging. The best improvement in durability was found in
Polymer composite the EN samples that contained dyes, such as Solvent Blue 97, Solvent Blue 104, Solvent Blue and Solvent
Accelerated aging Green 28. Moreover, the ability of solvent dyes to protect EN composites against harmful effects of solar
Stabilizer radiation was found to be much greater comparing to those of the investigated, commonly used
stabilizers.
2015 Elsevier Ltd. All rights reserved.

1. Introduction the media being colored. Out of the wide variety of dyes only a
small group of them is suitable for coloring polymers especially non
Dyes and pigments are widely used in the coloration of polymer polar like PP or PE. They must fulll a number of requirements such
materials for many commercial applications [1,2]. Although pig- as good solubility in non-polar or slightly polar media, light resis-
ments and dyes are primarily used to impart color to the particular tance, resistance to chemicals and high thermal stability under
polymer and make it attractive for consumers, they can also have a processing [18,19]. Some of the colorants which almost fully meet
dramatic effect on the polymer photostability [3e9]. For example, these requirements are solvent dyes being the subject of this study.
anatase form of titanium dioxide (TiO2) is markedly photosensitive Recently a new group of solvent dyes with anthraquinone
in degrading polymers [10]. Literature data showed that both chromophores, characterized by exceptional good heat and light
organic and non-organic pigments generally improve the light resistance has been developed. They are relatively inexpensive,
stability and weathering resistance of polymeric materials [1114]. have very good solubility in non-polar medium, excellent color
Favorable pigment inuences on the polymer light stability is most strength, transparency as well as high heat and light stability.
likely due to screening or selective absorption of harmful radiation, Moreover, a full range of colors, with similar solubilities and sta-
and deactivation of polymer photoexcited species. Among organic bilities, can be developed by changing the pendants on the
pigments, phthalocyanine blue and green pigments were identied anthraquinone molecule [20,21]. Nevertheless, in the literature
as the most useful in this regard, because they exhibit strong ab- there is no information about the effects of such type of dyes on the
sorption in UV range [15e17]. aging process of polymer materials.
Dyes as opposed to pigments, are soluble and transmit light in In the current research solvent dyes with anthraquinone chro-
mophores and different types of auxochromes, were employed to
obtain colored elastomer composites characterized by enhanced
* Corresponding author. aging resistance and good mechanical strength. The effects of
E-mail address: marzec.anna@hotmail.com (A. Marzec).

http://dx.doi.org/10.1016/j.polymdegradstab.2015.11.013
0141-3910/ 2015 Elsevier Ltd. All rights reserved.
138 A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145

solvent dyes on the properties of the tested composites were 5e15% for Eb values. The aging coefcient S was calculated ac-
compared to a reference sample and stabilizer-based composites of cording to the following relationship: S [TSA  EbA]/[TSB  EbB],
ethylene-norbornene EN, which are commonly used in polymer where TS corresponds to the tensile strength, Eb to the elongation
technology. at break, and TSA and EbA correspond to the values of the TS and Eb
after aging, respectively.
2. Materials and sample preparation Dynamic mechanical analysis (DMA) was performed on a TA
Instruments Q 800 Dynamic Mechanical Analyzer (USA) operating
Dyes: Solvent Blue 97, 1,4-bis[(2,6-diethyl-4-methylphenyl) in tension mode at a frequency of 10 Hz. Testing was conducted
amino] anthracene-9,10-dione (Keystone, USA), Solvent Blue, 104 over the temperature range of 80 to 100  C with a heating rate of
1,4-bis[(2,4,6-trimethylphenyl)amino] anthracene-9,10-dione 2  C/min.
(Keystone, USA), Solvent Green 28, 1,4-bis[(4-n-butylphenyl) The color of the obtained composites was measured using a CM-
amino-5,8-dihydroxy] anthracene-9,10-dione(Keystone, USA), Sol- 3600d spectrophotometer from Konica Minolta Sensing, Inc.
vent Red 207, 1,5-bis[(3-methylphenyl)amino]anthracene-9,10- (Japan). The instrument provided the color in the terms of the CIE
dione (Keystone, USA). Solvent Blue dye, 1,4-bis[(4-n-butylphenyl) L*a*b* color space system. In this color space, L represented the
amino] anthracene-9,10-dione has been synthesized according to lightness (or brightness), a and b were color coordinates, where a*
formulas described in the literature [21]. was the red direction, ea* was the green direction, b* was the
Commercial stabilizers: Tinuvin 234, phenol, 2-(2H-benzo- yellow direction, and eb* was the blue direction. Moreover,
triazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) (Ciba, Switzerland), changes in individual components allowed to estimate the total
Chimassorb 81, methanone [2-hydroxy-4-(octyloxy)phenyl]phenyl change of color E. The spectral range of the apparatus was
Switzerland (Ciba, Switzerland), Tinuvin 1577, 2-(4,6-diphenyl- 360e740 nm, where the change of color DE was calculated by the
1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (Ciba, Switzerland). equation below (1):
Structures of the studied dyes and stabilizers are shown in Table 1. q
Ethylene norbornene random copolymers (EN) e Topas Elas- DE
2
DL2 Da2 Db2 (1)
tomer 140 (40 wt% bound norbornene content, TOPAS Advanced
Polymers, Germany) was used as a polymer matrix. DL corresponds to the difference in the brightness intensity
The ethylene-norbornene EN mixtures were prepared by ho- between light and dark, Da corresponds to the difference of in-
mogenization of the EN copolymer and dyes or stabilizers in an tensity between green and red, Db corresponds to the difference of
internal mixer (Brabender Measuring Mixer N50). intensity between blue and yellow, and the D symbol implies the
The formulations of the EN compounds consisted of the difference in the colors of the samples before and after aging.
following: ethylene-norbornene copolymer (100 phr), solvent dye Weather aging of samples that contained dyes or stabilizers was
(0.2 phr) or stabilizer (0.2 phr). The polymer mixtures were pro- performed with light radiation of l 280e3000 nm using a Solar
cessed at a rotor speed of 50 rpm and an initial temperature of Climatic 340 instrument. The test was based on two variable pe-
80  C. Samples with a thickness of 1 mm were obtained by pressing riods that simulated day and night conditions. The test timeline had
the compounds between steel plates at 100  C for 10 min. the following parameters: day period e solar irradiation, temper-
ature 70  C, humidity 50%, duration 8 h; night period e tempera-
3. Method ture 20  C, humidity 60%, duration 4 h. The length of the test was
1400 h.
The thermal stability of the powders was studied using a TGA/
DSC1 (Mettler Toledo, Italy) analyzer. The samples were heated
from 25  C to 500  C in an argon atmosphere (60 ml/min) with a 4. Results and discussion
heating rate of 10  C/min.
The UVeVisible absorption measurement were studied with a 4.1. Thermal stability of dyes and commercial stabilizers
Jasco V-670 spectrophotometer (Japan), using standard quartz cu-
vettes. The absorption spectra were recorded over a wavelength Thermal analysis plays an important role in the study of the
range of 200e800 nm. The dyes and stabilizers concentrations stability of polymer additives. To be suitable for application, the
were 1  105 M for all the samples. dyes and stabilizers must be able to withstand the polymer pro-
Attenuated total reection Fourier transform infrared (ATR- cessing conditions and the subsequent environmental conditions.
FTIR) spectra were recorded on a Thermo Scientic Nicolet 6700 FT- Table 2 shows the thermal stability data of the dyes and stabilizers
IR spectrometer (USA), equipped with a diamond crystal, at room as determined by thermogravimetric analysis (TGA). The nature
temperature with a 32-scan signal from 600 to 4000 cm1 in and position of the substituents in the anthraquinone dyes inu-
absorbance mode. Each result was taken from 3 different places of ence the color and other properties. The heat and chemical stabil-
sample and averaged. ities vary considerably for different substituted pendants on the
DSC measurements (DSC1 Mettler Toledo, Italy) of samples were base anthraquinone chromophore. It is known that a-substituents
performed at a heating rate of 10  C min1 in the temperature increase the molar extinction coefcients and enhance the tech-
range 50 to 200  C under a nitrogen atmosphere. The glass nical performance, especially the lightfastness, of dyes because of
transition temperatures (Tg) were determined at the midpoint of their participation in intramolecular hydrogen bonding with the
the step. carbonyl groups. Generally, the heat stability of 1,4-disubstituted
Tensile properties were characterized with ZWICK 1435 tensile anthraquinone dyes, increases with the polarity of the substituent
testing machine of Zwick Roell Group (Germany). Tensile strength group [22,23].
(TS) and elongation at break (Eb) were measured at room tem- Solvent Green 28 has the highest heat resistance of the
perature with a crosshead speed of 500 mm/min. For testing, type 2 anthraquinone dyes with different substituents. The presence of
dumb-bell specimens were prepared according to the ISO-37-2005 hydroxyl groups in the 5- and 8-positions in the molecule of Sol-
standard. Five different dumbbell-shaped specimens were tested, vent Green 28 increases its thermal stability compared to Solvent
and the average value for each formulation was reported. Mea- Blue. On the other hand, the alkyl butyl chain attached to the aro-
surement error was in the range of 1e3 MPa for TS values and for matic ring in Solvent Blue provided better heat stability than the
A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145 139

Table 1
Chemical composition of the dyes and stabilizers studied.

Solvent Blue 97 Solvent Blue*

Solvent Blue 104 Solvent Green 28

Solvent Red 207 Solvent Yellow 163

Tinuvin 234 Chimassorb 81

Tinuvin 1577
*Experimental

methyl or ethyl groups in the ortho, meta and para positions (S. 200e800 nm. The absorption spectra of the studied compounds are
Blue 97, S. Blue 104). The order of stability of the anthraquinone shown in Fig. 1 and Fig. 2. The UV/visible spectral data for a series of
dyes is as follows: Solvent Green 28, Solvent Blue, Solvent Yellow anthraquinone dyes, which are given in Fig. 1 a, b and Fig. 2 a,
163, Solvent Blue 104, Solvent Blue 97 and Solvent Red 207. illustrate the effect of the substituent pattern on the color. The
Concerning the commercial stabilizers, the thermal resistance introduction of simple electron-donating groups into the anthra-
was the highest for the Tinuvin 1577, at approximately 336  C, and quinone dyes causes a bathochromic shift that is dependent on the
the lowest for stabilizer of the benzophenone group Chimassorb 81, number and position of the electron-donating groups and their
at 246  C. relative strengths. As it is known, the electron-donating groups
All investigated additives (dyes and stabilizers) can be used in exert stronger bathochromic effects in the a-positions (1-, 4-, 5-, 8-)
polymer technology, as their thermal stability is much higher than than the b-positions (2-, 3-, 6-, 7-) [24]. The green and blue dyes
temperature processing of most common polymer materials. exhibited absorbance in the UV (200e300 nm) and visible
(600e700 nm) regions. As shown in Fig. 2 a, the ethyl group
4.2. Spectrophotometric analysis of solvent dyes and stabilizers (eCH2CH3) that is attached to the phenyl ring of the Solvent Blue 97
dye endows it with higher UV absorbance than Solvent Blue 104.
The optical properties of the solvent dyes and commercial sta- The presence of hydroxyl auxochromes (eOH; 5, 8 position) in
bilizers were investigated by UV/Vis spectroscopy in the range of Solvent Green 28 molecules results in a bathochromic shift
140 A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145

Table 2
The results from thermogravimetric analysis of dyes and commercial stabilizers.

Dyes

Sample Start of degradation T (2%)  C T (10%)  C T (50%)  C Char residue at 500  C (%)

Solvent Blue 97 335 345 368 409 9.27


Solvent Blue 104 350 357 377 420 15.34
Solvent Blue 382 390 405 434 37.70
Solvent Green 28 407 415 433 462 44.00
Solvent Red 207 329 338 360 402 19.14
Solvent Yellow 163 357 368 388 437 25.85
Commercial stabilizers
Tinuvin 234 306 315 336 375 3.46
Chimassorb 81 246 256 276 376 3.39
Tinuvin 1577 336 345 368 410 3.75

(lmax 688 nm) and greater absorbance (hyperchromic shift) than properties of the samples were monitored over 1400 h of exposure.
the 1,4-disubstituted derivative of Solvent Blue (Fig. 1 b). Fig. 3 illustrates the changes in the mechanical properties of EN
The commercial UV absorbers considered in this study (Tinuvin composites that contain dyes and stabilizers as a function of the
234, Chimassorb 81 and Tinuvin 1577) exhibit absorption maxima aging time. The tensile strengths of all the samples decrease
in the UV A (315e400 nm) and UV B (280e315 nm) regions (Fig. 2 gradually with time (Fig. 3 a, b). As can be observed, the type of
b). Exposure to ultraviolet radiation in this range may cause sig- applied solvent dye or stabilizer was an important factor that
nicant degradation of the polymer materials. As was already controlled the lifetimes of the EN materials.
mentioned this stabilizers belong to UV absorbers class and are Before aging, the reference sample had a tensile strength TS of
used to preferentially absorb harmful UV radiation. A spectro- 39.1 MPa. However, degradation develops rapidly under aging
photometric study demonstrated that stabilizers absorb inten- conditions and leads to marked decreases in TS of approximately
sively in the most dangerous for polymers UV range 60% after 700 h of irradiation. What is more, the aging factor (S) was
(300e400 nm), whereas the anthraquinone solvent dyes, espe- much lower than 1 (after 700 h), what conrms the considerable
cially Solvent Blue 97, Solvent Blue 104, Solvent Blue and Solvent degree of degradation of this sample. The aging coefcient S was
Green 28, have maxima shift rather below 300 nm and above calculated from the ratio of the sample deformation energy and is
500 nm. combination of tensile strength and elasticity before and after aging
(Fig. 3 c, d).
4.3. Mechanical properties (static and dynamic) The initial mechanical properties of the EN/stabilizer compos-
ites were similar, and the differences become more prominent after
Polymer composites lose their mechanical properties during 700 h of weathering exposure. The TS values of the EN/Tinuvin 234
aging. Small changes in the chemical or physical structures can and EN/Chimassorb 81 composites decreased to 26.5 MPa and
cause intense variations in the mechanical properties of the com- 25.4 MPa, respectively.
posites. Thus, the estimation of mechanical properties, such as Fig. 3 (c, d) illustrates the aging of the investigated composites
tensile strength (TS) and elongation at break (Eb) during the aging as a function of aging coefcient S. The S values of samples that
process is important for evaluating polymer behavior during aging contain dyes with anthraquinone chromophores demonstrate
process. that the greatest improvements in the durability of EN were
Solvent dyes and stabilizer-based composites of EN were sub- provided by the addition of S. Blue 97, S. Blue 104, S. Blue and S.
jected to articial weathering and the variations in the mechanical Green 28.

Fig. 1. Absorption spectra of Solvent Blue 97 (a), Solvent Blue 104 (a), Solvent Green 28 (b) and Solvent Blue (b) in chloroform (c 1  105 M).
A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145 141

Fig. 2. Absorption spectra of Solvent Yellow 163 (a), Solvent Red 207 (a), Chimassorb 81 (b), Tinuvin 234 (b) and Tinuvin 1577 (b) in chloroform (c 1  105 M).

The investigated stabilizers (Tinuvin 234, Chimassorb 81 and lifetimes of the EN composites during aging.
Tinuvin 1577) exhibited worse protection of the samples during Fig. 4 shows the change of storage modulus (E0 ) and loss factor
weathering than some of the solvent dyes. The obtained results (tand) for reference sample and EN/Solvent Blue composite before
revealed that the application of anthraquinone dyes like S. Blue 97, and after 1400 h of irradiation. The change of the damping prop-
S. Blue 104, S. Blue and S. Green 28 signicantly prolonged the erties of materials during aging is due to changes in the polymer

Fig. 3. Tensile strength (a, b) and aging coefcients S (c, d) of EN composites that contain dyes and stabilizers as a function of the weathering time.
142 A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145

Fig. 4. Temperature dependence of the storage modulus E0 (a) and the tangent tand (c) at 10 Hz for EN and EN/Solvent Blue composites before and after 1400 h of aging.

Table 3 (Solvent Blue, Solvent Green 28) and the stabilizer Tinuvin 234
Characteristic values obtained from the DSC analysis of EN composites before and were studied using differential scanning calorimetry (DSC). The
after aging.
values of Tg and heat ow (expressed as the enthalpy DH) of the
Sample Tg from DSC/ C DH J g1 samples before and after aging are shown in Table 3 and Fig. 5
EN 1.8 55.7 (aec).
EN after 1400 h 2.5 60.3 The analysis of the EN composites before aging shows that the Tg
EN/Tinuvin 234 2.0 53.5 values of the Tinuvin 234 and solvent dyes are only slightly
EN/Tinuvin 234 after 1400 h 4.2 61.1
different from those of the reference sample. The application of
EN/Solvent Blue 1.3 54.4
EN/Solvent Blue after 1400 h 1.7 43.2 dyes and stabilizes did not affect the crystal phase; the enthalpies of
EN/Solvent Green 28 1.2 53.4 the studied samples ranged from 53.4 J g1 to 54.7 J g1. How-
EN/Solvent Green 28 after 1400 h 1.4 44.6 ever, signicant difference in the glass transition temperatures and
the content of the crystalline phase were present after 1400 h of
structure. The formation of a three-dimensional network by means aging.
of crosslinking leads to the decreases of the chain mobility and the The density and crystalline content of some of the polymers
maximum loss factor (tand max) [25]. increase at the beginning of degradation [26,27]. After 1400 h of
All of the composites exhibited higher stiffnesses after aging, weathering, Tg increased in the EN composites and EN/Tinuvin 234,
which is reected in the higher values of the storage modulus (E0 ). which was likely due to the increase in the crosslink density as well
The most signicant increase in E0 occurred in the reference sample as some changes in the crystal structure of the samples. Moreover,
(EN) after 1400 h exposure to weathering. Moreover, the curve that both composites showed increases in the crystalline phase content,
corresponds to the maximum loss factor shifted to higher tem- as the energies required for the phase transitions for EN and EN/
peratures after aging, and a decrease in the maximum loss factor is Tinuvin 234 increased to 60.3 J g1 and 61.1 J g1, respectively.
noted. In this case, DMA showed the most signicant variations in The behavior of the composites that contain dyes was different
the visco-elastic properties during outdoor exposure for the refer- after weathering. After 1400 h of exposure, the composites with
ence sample. This observation is consistent with the results ob- solvent dyes (Solvent Blue and Solvent Green 28) showed slight
tained from the static properties. Some of the variations in the glass reductions of the crystalline phase. It appears that the presence of
transition temperature (Tg) of the composites can be also related to this type of dye hinders the crystallization and formation of crystals
the changes in the polymer structure as a result of aging. during the aging process.

4.4. Differential scanning analysis of EN composites 4.5. Surface analysis e FTIR

The effects of aging on EN composites that contain selected dyes IR spectroscopic measurements allowed the carbonyl index to

Fig. 5. DSC curves of EN composites: pure EN (a), EN/Tinuvin 234 (b), EN/S. Green28 (c), before and after 1400 h aging.
A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145 143

Fig. 6. Carbonyl index (a, b) as a function of the weathering time of the EN composites that contain dyes and stabilizers.

Table 4 visible spectra in the CIELab color space was used to monitor the
Changes in the color parameters of EN composites that contain dyes after aging in discoloration process. Despite degradation during aging, as in the
the full solar spectrum.
case of colorless samples, such as EN and EN/stabilizer composites,
EN/composites Aging time [hours] DE DL* Da* Db* the color variations are only slightly noticeable compared to the
Solvent Red 207 700 18.67 6.85 11.18 7.29 dyed materials.
1400 23.28 7.23 13.03 8.08 Table 4 shows the differences in the DE, DL*, Da* and Db* values
Solvent Yellow 163 700 14.49 1.34 3.41 7.32 of EN/solvent dye composites subjected to weather conditions that
1400 22.05 3.03 5.07 12.21
showed the most signicant changes in color.
The results obtained for EN/S. Red 207 composites showed in-
be determined based on the ratio of the band intensity for the creases in DE* and substantial decreases in Da* over time. The co-
carbonyl group to the band intensity for the CeH group [28]. To ordinate a* exhibits increases in the red hue along the long positive
determine the aging progress and assess the effective lifetime of axis and the green hue along the long negative axis. In contrast,
the materials, components, or products, FTIR spectra were recorded progressive decreases in the b* value of EN/S. Yellow 163 composite
before, during, and after aging. indicate the degradation of yellow chromophores in the samples, as
Fig. 6 (a, b) shows the changes in the carbonyl indexes of EN the coordinate b* indicates an increase in the yellow hue along the
composites with different solvent dyes and stabilizers. The highest long positive axis and the blue hue along the long negative axis
values of the index after 700 h were obtained in the reference [29].
sample. The lowest intensities of the carbonyl group after 1400 h of The spectrophotometric measurements showed smaller
irradiation were detected in the EN composites containing S. Blue changes in color after 1400 h in the EN composites that contained S.
97, S. Blue 104, S. Blue and S. Green 28, which correlated with good Blue 97, S. Blue 104, S. Blue and S. Green 28. The analysis of the
mechanical properties. mechanical properties and surfaces shows that these samples also
exhibit the best resistance to aging. Fig. 7 (a, b) shows the variations
in the reectance spectra of EN/S. Yellow 163 and EN/S. Red 207
4.6. SEM and colorimetric measurements of EN composites
after 700 h of solar irradiation.
SEM was used to evaluate the effect of weathering on the sur-
Colorimetric analysis provides important data about color
faces of samples of pure EN and EN composites with Tinuvin 234
changes in materials, which can be related to the formation of
stabilizer or Solvent Blue 97 dye [30]. Fig. 8 (aef) shows micro-
oxidizing groups in the polymeric chains and/or the decomposition
graphs of the studied sample surfaces. Before weathering, the
of colorants that are incorporated in the polymer. A spectropho-
surfaces of the composites did not show any defect that would
tometric method that is based on calculating color differences from

Fig. 7. Change in reectance in EN composites that contain Solvent Red 207 (a) and Solvent Yellow 163 (b) after 700 h solar irradiation (b), line 1 e before aging, line 2 e after aging.
144 A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145

Fig. 8. SEM micrographs of (a) EN before aging, (b) EN after 700 h aging, (c) EN/Tinuvin 234 before aging, (d) EN/Tinuvin 234 after 700 h aging, (e) EN/S. Blue 97 before aging, (f) EN/
S. Blue 97 after 700 h aging.

indicate any degradation. Tinuvin 234 samples. The results show that the presence of Solvent
Numerous cracks were detected on the EN composites after Blue 97 makes EN less sensitive to degradation under solar
700 h aging, and the images show several differences. Cracks and conditions.
defects were observed mainly on the surfaces of the EN and EN/
Tinuvin 234 samples. Only minor cracks were observed on the EN/ 5. Conclusions
S. Blue 97 surface after this aging dose.
These data are in agreement with the mechanical properties In this research colored ethylene-norbornene composites with
that were obtained after 700 h solar irradiation. Less deterioration improved aging resistance were produced by addition of different
occurred in the EN/S. Blue 97 composite than in the EN and EN/ types of solvent dyes.
A. Marzec et al. / Polymer Degradation and Stability 123 (2016) 137e145 145

All tested dyes are able to withstand the processing conditions 18e23.
[13] J.C.V.P. Moura, A.M.F. Oliveira-Camposa, J. Grifths, The effect of additives on
of the polymers at temperatures greater than 300  C. Mechanical
the photostability of dyed polymers, Dyes Pigments 3 (1997) 173e196.
and surface analysis demonstrated that the samples containing [14] X. Wen, N. Tian, J. Gong, Q. Chen, Y. Qi, Z. Liu, J. Liu, Z. Jiang, X. Chen, T. Tang,
Solvent Blue 97, Solvent Blue and Solvent Green 28 dye were less Effect of nanosized carbon black on thermal stability and ame retardancy of
affected by aging factors comparing to EN composites with other polypropylene/carbon nanotubes nanocomposites, Polym. Adv. Technol. 24
(2013) 971e977.
dyes. The signicant improvement in the durability of the EN/sol- [15] P. Anna, Gy Bertalan, Gy Marosi, I. Ravadits, M.A. Maatoug, Effect of interface
vent dye composites might originate from ability of the dye to modication on the photo-stability of pigmented polyethylene lms, Polym.
absorb light and the high thermal stability of their particles. The Degrad. Stab. 73 (2001) 463e466.
[16] I.F.M. Major, G.M. McNally, A. Clarke, H. Ross, Effect of phthalocyanine blue
investigated stabilizers (Tinuvin 234, Chimassorb 81 and Tinuvin pigment on mechanical and thermal properties of polypropylene copolymers,
1577) exhibited a poorer protection of the samples during weath- Dev. Chem. Eng. Mineral. Process 12 (2004) 91e105.
ering than some of the studied dyes. [17] K. Hunger, Industrial Dyes: Chemistry, Properties, Applications, WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim, 2003, pp. 4e5.
These researches demonstrate that the presence of anthraqui- [18] R.M. Christie, Pigments, dyes and uorescent brightening agents for plastics:
none solvent dye can play two roles in EN composites, they provide an overview, Polym. Int. 34 (1994) 351e361.
intense colors at low concentrations as well as they provide [19] L.R.M. Christie, Colour Chemistry, Bookcraft Ltd, Manchester, 2001. Ch. 4.
[20] L.A. Bente, in: Plastics Additives, G. Pritchard (Eds.), Chapman & Hall, Bristol,
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better than some commercial stabilizers. [21] W. Polaczkowa, Preparatyka Organiczna, Warsaw, PWN, 1954, pp. 951e952.
[22] M.S. Zakerhamidi, A. Ghanadzadeh, M. Moghadam, Intramolecular and
intermolecular hydrogen-bonding effects on the dipole moments and pho-
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