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Polymer Degradation and Stability 133 (2016) 174e181

Contents lists available at ScienceDirect

Polymer Degradation and Stability


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

A renewable and compostable polymer for reducing consumption of


non-degradable plastics
Bahareh Bahramian, Ali Fathi, Fariba Dehghani*
The University of Sydney, School of Chemical & Biomolecular Engineering, Sydney, NSW 2006, Australia

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

Article history: Poly(propylene carbonate) (PPC) is a biodegradable and partially renewable polymer that is synthesized
Received 22 July 2016 from CO2. PPC is a suitable alternative to non-degradable polymers and a possible option for effectively
Received in revised form recycling CO2. In this study, the properties of PPC are compared with other commercial polymers. It is
23 August 2016
demonstrated that while the mechanical properties of PPC are comparable to non-degradable poly-
Accepted 27 August 2016
ethylene, its permeability to oxygen and water vapor are remarkably lower. PPC degradation in compost
Available online 29 August 2016
soil is nearly 9% within six months that is comparable with biodegradable polymers such as Eco-Flex.
Meanwhile, PPC is chemically stable when exposed to a broad range of simulated media such as low
Keywords:
Poly(propylene carbonate)
or high pH as negligible mass loss and molecular weight deductions are detected after six months
Biodegradable polymer exposure to these media. Therefore, PPC is deemed to be an ideal polymer for food packaging and many
Compostable other applications such as biomedical devices. The application of PPC can significantly reduce the
Packaging disposal of non-degradable polymers in landfills and minimize the reliance on fossil fuel based polymers.
© 2016 Published by Elsevier Ltd.

1. Introduction such as poly (lactic acid), for biomedical applications [7]. PPC's
degradation products are not acidic; this benign degradation
The broad use and application of non-degradable plastics in behavior in the body eradicates the risk of inflammation. However,
recent decades has led to major environmental issues, such as the the broad commercial application of PPC as a plastic has been
lowering capacity of landfills, and the exposure of the ecosystem to obstructed due to the low glass transition temperature (25e45  C)
hazardous pollutants [1,2]. As a results of this impact many coun- of the polymer [8].
tries has banned to use non-degradable polymer for food pack- In the previous attempts to increase the glass transition tem-
aging. Introducing biodegradable plastics, like Poly (propylene perature of PPC, the polymer was composited with different fillers
carbonate) (PPC), is deemed as a promising solution. Poly (pro- such as starch and cellulose [9,10]. For instance, the mechanical
pylene carbonate) (PPC) degrades enzymatically into water and CO2 properties of PPC-starch blends are comparable with polyesters and
that are non-hazardous. The polymer is synthesized by copoly- their composition can be tuned and varied for different applications
merization of CO2 and propylene oxide [3]. Converting CO2, that [7,11]. The addition of filler generally decreases the elongation at
attributes to the global warming into a biodegradable plastic with break, whilst enhancing the overall tensile strength. Low molecular
favorable properties can mitigate some of environmental issues interaction between PPC and the filler might result in heteroge-
arise from using non-degradable polymers [4,5]. neous distribution of the filler within the polymer structure and
PPC is produced in commercial scale by several companies such thus might be due to low elongation strength of the composite.
as Novomer and AZO-materials as a binder, plasticizer, and adhe- However, PPC-starch blends have increased water sorption and
sive [5]. PPC can also be used for the fabrication of agricultural hydrolysis and a tensile strength that is 20% greater than that of
mulches because of its biodegradability, transparency, and re- pure PPC [12]. This effect is attributed to a hydrogen bonding that
sistivity to moisture [6]. Our recent study showed the superior exists between the hydroxyl groups of starch and the carbonyl
properties of PPC when compared to polyester based polymers groups of PPC [7]. The interaction between PPC and starch can be
improved by using less polar derivatives of starch such as starch
acetate (SA) [13]. The tensile strength of PPC- 20 wt% SA is 50%
higher than neat PPC. In yet another study, the tensile strength of
* Corresponding author.
PPC was increased from 1.8 to 19 MPa and its Young's modulus was
E-mail address: fariba.dehghani@sydney.edu.au (F. Dehghani).

http://dx.doi.org/10.1016/j.polymdegradstab.2016.08.014
0141-3910/© 2016 Published by Elsevier Ltd.
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 175

enhanced from 201 to 1414 MPa by the addition of 1 wt% cellulose samples was 5 cm2 and Mocon self-adhesive foil masks were used
nanocrystals (CNCs) [14]. on both sides of films to seal each test specimen. Pure Oxygen were
In recent years Cardia Bioplastics has introduced a new type of applied in 30  C and dry condition (<3% relative humidity).
biodegradable plastic bag that is fabricated from a blend of PPC and water vapor transmission rate (WVTR): Mocon Permatran W 3/31
starch [15]. However, the hurdle for the broad application of this was applied to test WVTR of thin films (~500 mm) of polymers ac-
composite is the high level of metal based catalyst residue in PPC; cording to ASTM F 1249-06. The test area of samples was nearly
the acceptable threshold for metal catalyst according to the stan- 5 cm2. The analysis was conducted at 37.8  C (estimated tempera-
dards for compostable and biodegradable polymers is 150 ppm ture uncertainty ±0.5  C) and 90% RH for a period of 2 days.
[16]. We have recently developed a novel solvent free process that
tackled this issue and efficiently removed the level of metal resi- 2.5. Chemical resistance to food simulated media
dues to below the accepted level for composting [17]. With this
advancement, we are able to access several pathways for the future Polymer samples with the dimension of 5 mm  5 mm were
and wide-ranging applications of PPC and its derivatives. The aim of immersed in various food simulated media such as acidic (pH 4),
current study is therefore to assess the practical feasibility of using neutral (pH 7) and basic (pH 10) buffers, 50% ethanol/water solu-
PPC as an alternative plastic in different commodity products. To tion and edible olive oil for a period of 6 months at ambient con-
this end, the physico-mechanical properties of PPC alone and its dition. The media was changed on a weekly basis and samples were
composites are systematically compared with commercially avail- kept in sterile conditions to avoid the effect of microbial contami-
able plastics, e.g. low density polyethylene (LDPE), polybutyrate nation on degradation. The samples were removed from buffer
adipate terephthalate (Eco-Flex), and polyethylene/starch blend solutions at different time intervals and washed by milliQ water to
(commercial name: BLFO2). Primarily, the mechanical strength, remove all media residues and then were dried. The samples
biodegradability, chemical stability and high resistivity to oxygen incubated in olive oil were washed by ethanol prior to milliQ water
and water penetration were measured. to remove the residual of oil. Subsequently, the weight loss of
samples at each time point was recorded. Three samples were
2. Experimental collected at each condition to acquire statistically valid data.

2.1. Materials 2.6. Soil burial biodegradation

Poly(propylene carbonate) resin with the molecular weight of Soil burial biodegradation test was conducted in pots contained
463 KDa and poly dispersity of 2.03 was kindly supplied by Growth 10 cm mature compost soil made from food and garden organics
Technology International Pty Ltd. Eco-Flex and PE/Starch blend (containing active fungi, yeast, actinomycetes and Photosynthetic
(70% starch) with the commercial name of BLFO2 were supplied by Bacteria) sandwiched between 10 cm layers of wood chips to
Cardia Bioplastics Ltd. LDPE was purchased from Sigma-Aldrich. maintain the moisture content. Polymer films (thickness
Buffer solutions of pH 4, pH 7 and pH 10 were purchased from 800e1000 mm) with the dimension of 4 cm  4 cm were buried in
Ajax Finechem. Edible olive oil was used as fatty food simulated the middle part of the mature compost soil. The pots were main-
media. Cellulose powder (~50 mm), soluble starch powder tained in a controlled temperature and moisture incubator
(~200 mm) and Dimethylacetamide (DMAC) were purchased from (T ¼ 40  C, RH ¼ 60e70%). The relative humidity of the chamber
Sigma-Aldrich. Sodium chloride was supplied form Merck and the was controlled by using supersaturated sodium chloride solution
mature compost soil from Landtasia Organic Farms. and measured on a regular basis [19]. To avoid water loss by
evaporation, known amount of water was added to the soil every
2.2. Preparation of polymer films other day. Samples were removed from the soil to assess their
biodegradation rate in predetermined time intervals of up to 6
Thin films of each polymer (thickness 500e1000 mm) were months. After removal from the soil, samples were washed with
prepared by hot melt compression above their melting tempera- milliQ water twice to remove soil residue and dirt and dried in
ture (130  C for PPC, 150  C for Eco-Flex, LDPE and BLFO2, PPC-St vacuum oven until observing a constant weight. The degree of
50-50, PPC-Cell 75-25) and under the pressure of 10 kPa for PPC, biodegradation of samples at each stage was assessed by measuring
2 kPa for Eco-Flex, LDPE and BLFO2, and 7 kPa for PPC-St 50-50, their weight loss, surface morphology, molecular weight, tensile
PPC-Cell 75-25 in a period of 60 min for PPC, PPC-St 50-50, PPC-Cell properties and chemical structure.
75-25, and 20 min for Eco-Flex, LDPE and BLFO2.
2.7. Gel permeation chromatography (GPC)
2.3. Mechanical properties
The molecular weight of samples from biodegradation test was
The tensile test was conducted according to ASTM standard measured using the Gel Permeation Chromatography on a Shi-
using dumbbell shaped samples that were cut from polymer films madzu CBM-20A system with an Agilent Polargel-M guard column
(thickness 500e1000 mm). Universal testing instrument (Instron and three Phenomenex Phenogel columns using dimethyl acet-
5543) equipped with a 100 N load cell was used to measure tensile amide (Containing LiBr 0.03% w/w to avoid precipitation of the
strength of these samples. In addition, the tear resistance of spec- polymer) as a mobile phase at a flow rate of 1.0 ml/min at 50  C. The
imens were determined using Universal testing instrument (Ins- system was equipped with a Shimadzu RID-10A differential
tron 5543) equipped with a 100 N load cell. This test was conducted refractive index detector and Wyatt MiniDawn TREOS light scat-
using standard trouser-shaped test specimens [18]. tering. The GPC system was calibrated with narrow polystyrene
(PS) standards (PDI < 1.1).
2.4. Barrier properties
2.8. Nuclear magnetic response (1HNMR)
oxygen transmission rate (OTR): Mocon Ox-Tran 2/21 instrument
was used to conduct OTR analysis for thin films of polymers Chemical structure of PPC during the biodegradation test was
(~500 mm) according to ASTM D3985-05. The test area for the determined by proton nuclear magnetic response (1HNMR)
176 B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181

spectroscopy. Solutions of PPC in chloroform-d1(CDCL3) were 200


analyzed using a Burker NMR spectrometer (Varian 400 MR). The
180
A **
final molar ratio of functional groups was calculated based on the
integration of peaks. 160

Tensile Modulus (Mpa)


140

2.9. Scanning electron microscopy (SEM) 120

100
The surface morphology of PPC films from biodegradation and
chemical resistance tests was observed by the SEM (Zeiss ULTRA 80
Plus SEM) at 15 kV. Prior to this analysis PPC samples were 60
mounted on aluminum stubs, using conductive carbon paint, and
40
then gold sputtered using the Emitech K550X sputter coater.
20

2.10. Statistical analysis 0


Eco-Flex BL-FO2
BLFO2 LDPE PPC
Data is reported as mean ± STD. One way analysis of variance 16
(ANOVA) is performed using Excel for single comparisons. Statis- B **
tical significance was accepted at p < 0.05 and indicated in the
14 **
Figures as * (p < 0.05), ** (p < 0.01) and *** (p < 0.001). 12

Ultimate Strength (MPa)


10
3. Results and discussion
8
The mechanical properties, degradation rate, permeability to
oxygen and moisture and resistivity to chemicals are the main 6
characteristics that commonly are measured for assessing the
application of a polymer, particularly for food packaging. We 4
measured these properties of PPC and compared them with poly-
mers such as LDPE and Eco-Flex that are broadly used. 2

0
3.1. Mechanical properties Eco-Flex BL-FO2
BLFO2 LDPE PPC
120
The mechanical properties are critical in the selection of poly- C
mers for different applications. Any impact during the handling,
100
*
shipment and storage of food may affect the safety and the quality
Tear Resistance (N/mm)

of the final product. An important parameter in food packaging is


tensile strength as it determines the maximum load a material can 80
withstand under elongation until it ruptures. The results in Fig. 1A
demonstrate that the tensile modulus of PPC was three-fold higher 60 **
than biodegradable Eco-Flex polymer and it was within the same
range as non-degradable LDPE. The ultimate strength of PPC was
significantly higher than LDPE and Eco-Flex (Fig. 1B). Additionally, 40
the durability of the polymers against the tear force and growth of
any crack under tension force are of great importance. The results 20
presented in Fig. 1C show that the tear resistance of PPC was nearly
five-fold higher than LDPE and significantly higher than BLFO2.
0
These data confirmed that PPC films have comparably better tensile LDPE
Eco-Flex PPC PE BLFO2
properties than the most commonly used biodegradable and non-
degradable polymers. Fig. 1. A) Tensile modulus, B) ultimate strength, and C) tear resistance of different
polymers.

3.2. Barrier properties


3.3. Chemical resistance in food simulated media
The barrier property of a material used in packaging or medical
devices plays a critical role on a product's shelf life. For example, It is pivotal to determine the chemical resistance of a polymer,
small molecules, such as oxygen and water vapor may permeate particularly, a packaging material in different simulated conditions.
through a polymer and adversely impact on the safety and the For instance, the residue of polymer degradation might have a
quality of the contents [20]. Our study illustrates the superior negative impact on food safety and quality [20]. Our previous study
barrier properties of PPC. The results in Fig. 2 demonstrate that the demonstrated slow degradation of PPC compared to PLA in buffer
oxygen transmission rate (OTR) and water vapor transmission rate solution [7]. Upon the addition of enzymes such as a-amylase and
(WVTR) through PPC were lower than LDPE and Eco-Flex. There- lipase in the buffer solution the degradation of PPC was only 9%
fore, application of PPC for food packaging can potentially reduce within eight weeks [20]. In this study, food simulated media are
the risk of food oxidation and preserve food quality by reducing the used to further examine the degradation of PPC and its chemical
rate of water loss or absorption.
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 177

food products. The hydrophobic nature of PPC and its chemical


resistance make this polymer more suitable for packaging
compared to renewable and natural based polymers such as starch.

3.4. Soil burial biodegradation

The biodegradation and composting rate of a polymer is gov-


erned by several factors such as molecular weight, surface area,
concentration and type of additives, bacteria composition and
condition of the soil [22]. Previous studies reported 4% mass loss of
PPC films (MW ¼ 50e65 KDa, thickness ~ 40e50 mm) buried under
enriched garden soil for six months [23]. However, the result of
another study in the standard composting condition for a 300 mm
film of PPC with high molecular weight of 670 KDa demonstrated
considerable decomposition of 63% after nearly three months [22].
Such a broad discrepancy in the degradation rate reported for PPC
most likely due to different experimental conditions, i.e. variation
in PPC characteristics, types of soil, microorganisms and enzymes
presented in different studies. Accordingly, we assessed the
biodegradation rate of PPC and other polymers at standard condi-
tion to avoid any inconsistency. The degradation behavior of these
polymers were compared in two different soil types including
sterilized garden soil and compost soil at a controlled temperature
and moisture content (40  C, 50% RH). In the case of sterilized
garden soil, less than 10% mass loss was measured for BLFO2
(p < 0.01), and no degradation was observed for PPC, LDPE and Eco-
Fig. 2. Comparison of A) OTR and B) WVTR of PPC with other commercial polymers. Flex after six-month burial at the same temperature and relative
humidity condition (p > 0.05). The small degradation rate for BLFO2
was solely due to hydrolysis of starch.
resistance [21]. PPC films were placed in different media such at pH The degradation of PPC and other polymer samples was signif-
4, 7 and 10, 50% (v%) ethanol and edible oil. The physico-chemical icant when they buried under non sterile compost soil. As the re-
properties of samples were then analyzed by using gravimetric sults in Fig. 5 demonstrate, the mass loss of BLFO2 films was nearly
technique, SEM, GPC and NMR analyses. 80 wt% after six months due to the presence of starch in their
After six months incubation at ambient conditions, no signifi- structure that is a hydrophilic and biodegradable polymer. None-
cant mass loss was observed for PPC, as well as commercial LDPE theless, no significant mass loss was observed for pure LDPE films.
and Eco-Flex (p > 0.05) when exposed to different media. On the In addition, mass loss of PPC films was nearly 8% within six months,
other hand, the results in Fig. 3 show that while mass loss for BLFO2 which was slightly lower than the biodegradable Eco-Flex. PPC
films was negligible in fatty media, it was nearly 7% within six degradation rate in soil was comparable with the value acquired
months period in other media such as acidic, alkaline, and alco- from our previous study using a buffer solution that contained
holic. This mass loss is due to the hydrophilic nature of starch in the enzymes (110 U/L from Rhizopus oryzae). It can be concluded that
structure of BLF2. the soil composition and its microbial level have paramount im-
In addition, results in Fig. 4 demonstrate negligible effect on pacts on the PPC biodegradation rate. Therefore, the enzymatic
surface morphology of PPC after this test. GPC analysis showed that reaction plays a key role in breaking the PPC polymer structure and
the molecular weight of PPC did not change within this period of its degradation.
incubation in food simulated media (p > 0.05). PPC therefore can be Gel permeation chromatography (GPC) was conducted to
used alone or as a coating polymer for packaging a broad range of investigate the impact of degradation on the average molecular
weight and poly-dispersity index (PDI) of PPC films. As shown in
Fig. 6 and Table 1, the GPC chromatogram of PPC was gradually
broadened by increasing the degradation period. In addition,
8 average molecular weight of PPC was decreased and the PDI was
7 elevated. As an illustration, after six months the PPC molecular
weight was reduced nearly 15%. These results confirmed the
6
weight Loss (%)

breakdown of PPC in the molecular level and showed the seg-


5 mentations of random units from the large polymer chains. The
microscopic images of polymer films at different time points during
4
the biodegradation test are presented in Fig. 7. As it was anticipated,
pH4
3 pH7 the degradation of polyethylene films during six months period
2
pH10 was negligible. However, the surface of BLFO2 films was substan-
x 50% Ethanol
tially degraded and both PPC and Eco-flex films were degraded
1 * Olive Oil
gradually during this period. Furthermore, the SEM images of PPC
0 films in Fig. 7. E endorsed the appearance of erosion on the surface
0 50 100 150 200 of these samples after six months.
1
Time (day) HNMR analysis was conducted on PPC films at different time
intervals post-soil burial degradation study to further study PPC
Fig. 3. Degradation of BLFO2 films in various media within six months period. degradation mechanism. The results in Fig. 8 demonstrate chemical
178 B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181

Fig. 4. SEM images of the PPC films A) before incubation and after 6 months incubation in B) acidic, C) basic and D) 50% ethanol E) fatty food simulated media.

90 Table 1
Molecular weight and PDI of the PPC films before and after soil burial
80 LDPE biodegradation.
PPC
70 Eco-Flex PPC sample Mw PDI
Weight Loss (%)

x BLFO2
60 Control (month 0) 463,746 3.26
Second months 417,026 4.69
50 Third months 409,809 5.58
Sixth month 394,721 6.23
40

30

20 The 1H NMR spectra of PPC samples showed that after degradation,


the ratio of b/d was significantly decreased. The biodegradation of
10
PPC is due to the breakdown of the carbonate linkages in the
0 polymer backbone. The gradual reduction in the ratio of in-
0 50 100 150 200 tegrations at (4.18, b), and (3.56, d) endorsees the carbonate linkage
Time (Day)
breakdown in the polymer backbone. For example, b/d ratio was
Fig. 5. The weight loss of polymer films in compost soil as a function of time.
decreased from 14.41 at first day to 13.50 and 12.11 after one and six
months, respectively.
A tensile test was conducted to assess the impact of degradation
on the mechanical strength of PPC films. As depicted in Fig. 9, PPC
PPC (Month 0) tensile modulus decreased nearly 45% after six months degradation
Month 2
Month 3 in soil. In fact, this drop of mechanical strength was attributed to
Month 6
the gradual reduction of molecular weight and the degradation of
PPC chemical structure. The conversion of large molecular chains
with carbonate linkages to the short chains with ether linkages has
a direct impact on the mechanical properties of PPC.

3.5. Effect of addition of renewable natural polymers on the


properties of PPC

15 17 19 21 23 25 27 We attempted to blend PPC with cellulose and starch, two


RetenƟon
RetentionTime (min)
Time (min) renewable natural polymers, to promote the mechanical properties
of PPC and to enhance its degradation rate. Our preliminary results
Fig. 6. GPC chromatograms of PPC samples before and after soil burial biodegradation.
showed that homogenous blends were achievable when the com-
positions of starch and cellulose microparticles in PPC were below
50 wt% and 25 wt%, respectively. These compositions are the
shifts of PPC after biodegradation: 1H NMR (CDCl3), 1.31 (3H, CH3),
maximum amount of starch and cellulose that could be added to
4.18 (2H, CH2CH), 4.98 (1H, CH2CH) for carbonate structure (n) [24],
PPC to maintain homogeneity, desirable mechanical properties and
and 1.14 (3H, CH3), 3.56 (2H, CH2CH), 3.40 (1H, CH2CH) for ether
also higher degradation rate. The addition of both starch and cel-
structure (m) [25]. The ratio of integrations at (4.18, b) and (3.56, d)
lulose to PPC enhanced the tensile modulus of PPC remarkably as
were compared to assess the effect of biodegradation on PPC films.
depicted in Fig. 10. However, these natural polymers had negligible
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 179

Fig. 7. The images of A) PPC, B) LDPE, C) Eco-flex, D) BLFO2 and E) SEM images of PPC films at different time points of soil burial.

Fig. 8. 1H NMR spectra of PPC in A) day 1 and B) month 6 of soil burial.


180 B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181

250 forth. Therefore, these blends could not be used for the applications
** in which the high tear force is critical. However, the lower amount
200 of starch in composite may have less impact on this property of PPC.
Tensile Modulus (MPa)

For instance, the tear resistance of PPC-10% starch is 42.4 ± 0.18 N/


mm, more than four-fold higher than the PPC- 50% starch blend.
150
We examined the presence of starch and cellulose on the PPC
chemical resistance when placed in different media. The results in
100 Fig. 11 show that degradation of PPC films that contained 50 wt%
starch and 25 wt% cellulose were 1% and 3%, respectively during six
50 months in various aqueous media such as acidic, basic, neutral and
alcoholic. However, the degradation of both blends in oil was
negligible. Nevertheless, pure PPC films were chemically resistant
0
PPC Month 3 Month 6

Fig. 9. Tensile modulus of PPC films during the biodegradation test.


5
pH4
pH7 A
impact on the ultimate strength of PPC. On the other hand, as 4 pH10
x 50% Ethanol

weight Loss (%)


shown in Fig. 10C, the presence of starch and cellulose had an
adverse effect on the tear resistance of PPC. In fact, the addition of 3 * Olive Oil

50% starch significantly decreased the tear resistance of PPC to one

2
1000
900 A ** * 1
800
Tensile Modulus (MPa)

700 0
600 0 50 100 150 200
500 Time (day)
5
400 pH4
pH7 B
300
4 pH10
200 x 50% Ethanol
weight Loss (%)

100
3 * Olive Oil
0
PPC PPC-St 50-50 PPC-Cell 75-25
18 2
16
B *
14 1
Ultimate Strength (MPa)

12
10 0
0 50 100 150 200
8
Time (day)
6
Fig. 11. Degradation of A) PPC-St 50e50 and B) PPC-Cell 75-25 films in various media
4
in six months period.
2
0
PPC PPC-St 50-50 PPC-Cell 75-25 60
PPC
80 PPC-Cell 75-25
C ** 50 x PPC-St 50-50
Weight Loss (%)

**
Tear Resistance (N/mm)

60 40

30
40

20

20
10

0 0
PPC PPC-St 50-50 PPC-Cell 75-25 0 50 100 150 200
Time (Day)
Fig. 10. A)Tensile Modulus, B) Ultimate Strength, and C) Tear Resistance of PPC and PPC
composites with natural polymers. Fig. 12. The weight loss of polymer films in compost soil as a function of time.
B. Bahramian et al. / Polymer Degradation and Stability 133 (2016) 174e181 181

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