Polymer Degradation and Stability xxx (2017) 1e14

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Polymer Degradation and Stability

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Degradation of polymer blends: A brief review

F.P. La Mantia a, *, M. Morreale b, L. Botta a, M.C. Mistretta a, M. Ceraulo a, R. Scaffaro a
a
di Palermo, Dipartimento di Ingegneria Civile, Ambientale, Aerospaziale, Dei Materiali e Viale Delle Scienze, 90128 Palermo, Italy
Universita
b
di Enna “Kore”, Facolta
Universita
di Ingegneria e Architettura - Cittadella Universitaria, 94100 Enna, Italy

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

Article history: The usefulness of any material, including polymer blends, depends on its degradability and durability.
Received 29 March 2017 The blend composition can significantly affect the degradative behavior of a polymer blend and can differ
Received in revised form from the degradation routes of the pure components since the interactions among different species in
14 June 2017
the blends during degradation, and among the degradation products, can occur. These reactions can lead
Accepted 10 July 2017
Available online xxx
either to an acceleration of the degradation rate or to a stabilizing effect in comparison with the pure
components. Thus, the additive rule cannot be often applied in case of degradation of polymer blends
and, therefore, it is difficult to predict the degradative behavior of a polymer blend on the base of the
Keywords:
Polymer blends
properties of pure components.
Compatibilization This review aims to report the status of the research on degradation of polymer blends focusing on
Thermal degradation thermal, thermomechanical and photo-oxidative degradation.
Photooxidation © 2017 Elsevier Ltd. All rights reserved.

1. Introduction many years ago, this topic considering thermal, thermomechanical

The history of polymer blends is quite long and strictly corre-
lated with that of polymers themselves. Indeed, blending two or
more polymers may give rise to new polymeric systems with new,
interesting and “ad hoc” properties, different from those of the two
components, thus eliminating the long and expensive route of
synthesizing new polymers [1e9]. Nevertheless, an important
shortcoming in blending different polymers is that the polymers
often form immiscible and incompatible blends, displaying a coarse
morphology with particles of dispersed phase badly adherent to the
matrix and badly distributed. Consequently, a compatibilization
process is necessary in order to modify the interfacial properties in
immiscible polymer blend, thus leading to a reduction of the
interfacial tension coefficient and the formation and stabilization of
the desired morphology [10e21]. Several compounds have been
used as compatibilizers including, more recently, nanoparticles that
can modify the final morphology of the polymer blend [22e32].
A recent outstanding book [33] outlines the behavior of many
polymer blends used in several applications, or just investigated.
In spite of this important industrial and academic interest in
polymer blends, relatively few papers have been published on the
degradation of these polymer systems. La Mantia [34] reviewed,
* Corresponding author.
E-mail address: francescopaolo.lamantia@unipa.it (F.P. La Mantia).
and photo-oxidative degradation of a number of polymer blends. A
few years later, a review on the thermomechanical degradation has
been also published by La Mantia and Valenza [35] and, more
recently, by Matusinovic and Wilkie [36] as well as Vikhsah and
Nazarenko [37] who reviewed only the thermal degradation of
these systems.
This review covers, in particular, the literature published on the
degradation of polymer blends starting from the previous reviews
[34e37], paying particular attention on thermal, thermomechan-
ical and photo-oxidative degradation.
2. Basic concepts on the degradation of polymer blends
The degradation routes of single polymers should be essentially
attributed to the formation of macromolecular radicals, due to the
action of some external driving force (temperature, mechanical
stress, radiations, etc) and to the subsequent reactions of such
radicals with both the polymer macromolecules and oxygen. The
so-formed unstable oxygenated species evolve towards the for-
mation of stable macromolecules with oxygenated groups and
gives rise to a dramatic change of the molecular structure (molec-
ular weight, polydispersity, branching, etc); more in details,
decrease of the molecular weight, possible presence of branching
and, in a few cases, formation of cross-linked structures occur. The
latter case occurs mainly in the degradation of polyethylenes, while
other polymers typically evolve towards a decrease of the

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Please cite this article in press as: F.P. La Mantia, et al., Degradation of polymer blends: A brief review, Polymer Degradation and Stability (2017),
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2 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14
molecular weight. The presence of two or more polymeric phases in
a blend strongly changes this already complex scheme. Indeed, the
macroradicals of both components (in a two-components blend)
formed at the beginning of the degradation process may react even
between them, or with the macromolecules of the other phases.
Different paths may be followed during degradation, as here
summarized:
- reactions between macroradicals and macromolecules (I)
- reactions between two different macroradicals (II)
- reactions between macromolecules and small molecules (III)
- reactions between macromolecules and small radicals (IV)
- reactions between macroradicals and small molecules (V)
- reactions between two small molecules (VI)
Then, these reaction may give rise to more complex degradation
paths characterized by many competitive reactions, with the for-
mation of chemical species that can strongly alter not only the
degradation scheme itself, but also the effect of the degradation on
the final properties of the blend. For instance, the possible reactions
between macroradicals of the two components or with the mac-
romolecules (reactions I and II), may give rise to copolymers which,
in turn, may act as compatibilizers between the two components,
thus improving the properties of the polymer blend while the
degradation leads to a worsening of the properties. The reactions
between small molecules or radicals with the macromolecules of
the other component (reactions III and IV) can give rise both to
faster breaking of the macromolecules or to chemical species able
to stabilize the blend. Then, a pure polymer, stable in the presence
of external driving forces and then not undergoing any degradation
phenomena, may undergo degradation even in the same condi-
tions, when involved in a blend with a less stable polymer, because
the macroradicals formed from the second polymer phase can
extract a hydrogen atom from the macromolecules of the first
polymer, thus causing the formation of a macroradical. On the
contrary, the reactions among the different chemical species, which
can occur both in the bulk and at the phase boundaries, can lead to
some stabilizing effect with respect to the degradation kinetics.
3. Thermal and thermomechanical degradation
Thermal degradation can be defined as the process a polymer
blend undergoes, in inert atmosphere, because of the action of heat.
The effects can be very different depending on the components of
the blends and, in turn, on their chemical structure. In general,
thermal stresses result in the formation of decomposition (ther-
molysis) products which, depending on blend components, their
relative amounts and the temperature, may initiate the degradation
of the blend or, on the contrary, act as stabilizers [33,38,39]. Syn-
ergistic (and thus, desirable) effects are present when the resis-
tance to thermal degradation of the blend is higher than that of the
individual components [33]. In presence of oxygen (and thus, of
air), thermo-oxidative degradation occurs; when also mechanical
stress (typically, during processing) is involved, degradation is
referred to as “thermomechanical”.
Table 1 reports the degradation conditions and the main results
of several works on the thermal and thermomechanical degrada-
tion of polymer blends.
One of the first polymer blend categories which should be taken
into account is represented by polyolefin blends; polyolefines
mainly include ethylene-based and propylene-based macromo-
lecular chains, but also olefin-based elastomers [33,40]. In general,
the most used polyolefins, polyethylene (PE) and polypropylene
(PP) are incompatible and immiscible each other [33].
The scientific literature does not report much data on studies
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about compatibilization of the aforementioned polyolefines,
focusing on blends with completely different polymers instead. For
instance, Gonzalez at al. [41]. studied the thermal decomposition of
blends of polyamide 6 (PA6) with PP and PP functionalized with
diethylmaleate (DEM) (PP-g-DEM). They found that, while PP leads
to a decrease of the thermal decomposition starting temperature,
the use of functionalized PP strongly mitigates this decrease; this
leads to a blend with thermal stability reportedly similar to that of
PA6 and easier to process than neat PA6. The highest thermal sta-
bility was found in PA6/PP1-g-DEM blends at 70/30 wt/wt
composition. George et al. [42] investigated on the thermal and
crystallization behavior of isotactic polypropylene/nitrile rubber
(NBR) blends via thermogravimetric method. It was found that the
incorporation of NR into PP increased the initial degradation tem-
perature of PP (the lowest degradation temperature between the
various blends was found in the 50/50 wt/wt ones); furthermore,
the weight loss at given temperatures was decreased upon
blending. They also investigated the possible compatibilization of
the blends using phenolic modified polypropylene and maleic an-
hydride modified propylene, finding an increase of the degradation
temperature and a decrease of the weight loss.
Another interesting point of view is related to the behavior of
LDPE/HDPE blends, provided that these two polyolefins can be
easily found in plastic waste and can thus affect the post-consumer
recycling process. For instance, Suarez et al. [43] developed a two-
step process for recovering plastic residues containing partially
degraded LDPE and HDPE, resulting in a 75/25 LDPE/HDPE blend:
this was exposed to low doses of 60Co gamma radiation, obtaining
an improvement in the mechanical properties (elastic modulus and
maximum stress) due to partial crosslinking; melting and crystal-
lization temperatures decreased upon increasing the radiation
dose.
More recently, Jose et al. [44] studied the thermal degradation
behavior of polyamide12/isotactic polypropylene (PA12/PP) blends
via thermogravimetric method, with and without PP grafted with
maleic anhydride (PP-g-MA) as compatibilizer. It was found that
the blend ratio as well as the presence of the compatibilizer had
significant effects on the thermal stability of the blends: the addi-
tion of 30% PA12 into PP lead to an improvement of the thermal
stability (as PA12 is more stable), while no significant variations of
the latter was found with inverted percentages; these results were
attributed to the blend morphology. Consequently, the presence of
the stabilizer significantly affected the thermal stability; optimum
behavior was shown by PA12-PP 70-30 blends, followed by 50-50
ones.
Mourad et al. [45] studied the behavior and thermal stability of
VLDPE/iPP blends, either previously subjected to aging (in oven at
100
C from 2 up to 14 days) or not. Thermal aging showed to give
no effects on the thermal behavior of neat polymers and their
blends, except for the melting temperature, which increased with
the aging time. TGA in nitrogen showed that none of the prepared
blends started to decompose at temperature lower than 380
C and
that the thermostability of PP was higher than that of LDPE and
related blends; however, both TGA and FTIR analyses showed that
thermal treatment in oven did not significantly affect the chemical
integrity of the blends.
The literature also reports significant results concerning PVC-
containing blends. Ishiaku et al. [46] studied the mechanical and
thermo-oxidative behavior of blends of PVC and epoxidized natural
rubber (ENR)and acrylonitrile butadiene rubber (ABR). More in
details, both rubbers are polar and compatible with PVC; their
degree of compatibility was therefore investigated by comparing
the mechanical properties of 50/50 blends (with PVC) of the two, as
well as their response to thermo-oxidative aging. They found that
the blends containing ENR showed mechanical properties
 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14 3

Table 1
Synoptic table on thermal/thermomechanical degradation of several polymer blends.

Polymers Blend composition Compatibilizers/ Processing Degradation conditions Degradation outcomes Ref.
Additives

PA6/PP 10,20,30,50,60,70, PP1-g-DEM in twin screw extruder at TGA, samples heated up PP leads to a decrease of [41]
80 wt% replacement for PP 264
C and 55 to 773 K the thermal
r.p.m. 10
C/min, in N2 decomposition starting
atmosphere temperature; PP1-g-DEM
mitigates the decrease
iPP/NBR 30, 50, 70 wt% MA-PP; Ph-PP; 1 to 15 wt melt mixing at 180
C, TGA from 30 to 600
C at initial degradation [42]
%; only for 30% blends 60 rpm, 10 min 10
C/min in N2 temperature of PP
atmosphere increased, and weight
loss decreased, upon
blending with NBR;
compatibilization
increased the
degradation temperature
LDPE/HDPE 75/25 wt/wt e Irradiation with gamma TGA from 10 to 170
C improvement in the [43]
rays on recycled LDPE/ at mechanical properties
HDPE 10
C/min in N2
atmosphere
PA12/PP PA12/PP ¼ 90/10, PP-g-MA (1e20%) Mixing at 185
C, 60 rpm, TGA from room Best improvement in [44]
80/20, 70/30, 60/40, 6 min þ compression temperature to 600
C at thermal stability
50/50, 40/60, 30/70, molding at 190
C 20
C/min in N2 shown by PA12/PP 70/30,
20/80 and 10/90 atmosphere followed by 50/50
VLDPE/iPP 25/75, 50/50,75/25 e Injection molding; aging TGA from room Thermostability of PP [45]
in oven at 100
C for 2 up temperature to 600
C at higher than PE and their
to 14 days 10
C/min in N2 blends; thermal
atmosphere treatment in oven at
100
C did not affect the
chemical integrity of the
blends
PVC þ ENR 50/50 TMQ (antioxidant), Mixing at 150
C, 50 rpm, Aging at 100
C for 7 days ENR blends with [46]
PVC þ ABR Calcium stearate 6 min þ compression mechanical properties
(3 phr) molding similar to ABR blends but
more prone to oxidative
aging; TMQ mitigated
this: stearate effective
only for ABR blends
PVC/EVA 50/50 wt% e TGA up to 600
C, at all of the blends showed [47]
different rates (5-10-15- autocatalytic effects; EVA
20
C/min) with higher VA contents
showed reduced
degradability in
comparison to those with
lower VA-containing
EVAs
PVC/PVB 95/5, 90/10, 85/15, Ba-Cd-Zn stearate Solvent casting in THF TGA in N2, 10
C/min, thermal stability of the [48]
80/20, 75/25, 70/30, n-OTM from room temperature blends increased on
65/35, 60/40, 55/45, DBLC to 200
C; rate of increasing the PVB
50/50, 40/60, 30/70, dehydrochlorination content;
20/80, 10/90 By potentiometric
determination of the
evolved HCl gas at 180
C
in air.
PVC/PDPS 3:1,1:1,1:3 e Solvent casting in THF TGA in N2, 10
C/min, up slight destabilization at [49]
PVC/PDMDPS to 600
C; low loading of PDPS and
PDMDPS; with 50% PDPS
and PDMDPS(or more):
stabilizing effect,
especially in the PDMDPS
blends (slower weight
loss)
PVC/PMMA 3,5,8,10,15,20 wt% e Solvent casting in THF TGA in N2, from 2.5 to thermal decomposition [50]
25
C/min, from ambient temperatures increased
to in presence of PMMA;
700
C higher stabilizing effect at
10 wt% PMMA content
PVC/PANI 99/1,97/3,95/5 3-(4-bromophenylazo)- Solvent casting in THF TGA in Argon or air, 10 Thermal stability [51]
9-(2,3-epoxypropane) and 50
C/min depends mainly on
carbazole composition; HCL from
PVC degradation
specifically reacts with
PANI structures
(continued on next page)

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Table 1 (continued )

Polymers Blend composition Compatibilizers/ Processing Degradation conditions Degradation outcomes Ref.
Additives

Nylon6/ACM 40/60, (50/50, 60/40) e Mixing at 220
C, TGA in N2, 20
C/min, Blends [52]
wt/wt 40 rpm þ compression from ambient temp. to degrade at a lower
molding at 230
C 600
C temperature compared to
nylon-6; mechanical
properties do not
significantly deteriorate
up to 150e200
C
nylon 100:0, 90:10, e Melt blending in co- TGA in N2, 10, 20, 30, and activation energy and [53]
66/EPR-g-MA 80:20, 70:30, 60:40 rotating twin-screw 50
C/ reaction order of thermal
wt/wt extruder, 100 rpm, 250- min, up to 550
C degradation decreased
260-270,- upon increasing the
280
C þ compression rubber content
molding at 260
C
PET/PLA 90/10, 50/50 e Solution method TGA in air, 5-10-15-20
C/ degradation rate [55]
min, from room increased, while
temperature up to 600
C degradation activation
energy decreased, on
increasing PLA content
PET/PLA % PLA ¼ 0.5,1,2,5, e Injection molding TGA in N2, 10
C/min, Decrease of the onset [56]
10,20 from 50 to temperature of
650
C degradation, especially
for PLA wt% > 5%
PC/ABS 55/45 e Melt mixing, T ¼ 230, Mixing; annealing in N2 Melt viscosity decreasing [57]
250, 270
C, rotor at 250
C upon increasing the
speed ¼ 30-50-70
C, mixing temperature;
mixing time 1-2-5-7- annealing led to changes
10 min in blend morphology
EPDM/SAN/ 60/10/30 (approx.) e Radical solution TGA in air, 10
C/min, Oxidation starts on the [58]
EPDM-g-SAN copolymerization from room temp. to EPDM chains;
of styrene and 600
C crosslinking occurred
acrylonitrile in simultaneously with
presence of EPDM rubber chain scission and
destruction of the graft
structure
HIPS/SBS 90/10; 45/55 e Twin screw extruder DSC, isothermal thermal Degradation rate [59]
(150-200-200-150
C, oxidation at 150-155- increases on increasing
60 rpm) þ compression 160-165-170
C, in air the SBS content
molding (230
C)
NR/EVA EVA content ¼ 0, EVASH; DCP Two-roll mill at 130
C, TGA in N2, 20
C/min, up Decrease of molecular [60]
20, 40, 60, 80, 30 rpm to weight and mechanical
100 phr 550
C; SEC performance mitigated
by EVASH
PMMA/PSD 90/10, 80/20, e Solvent method in TGA in N2, 10
C/min; PSD and PST stabilized [61]
PMMA/PST 70/30 chloroform direct pyrolysis- the PMMA degradation
massspectrometric(DP-
MS) analysis
PS/PSSNa From 2.8 to 29.9 e Mixing at 150
C, 30 min TGA at 20
C/min under Blends showed enhanced [62]
mol% SSNa N2, up to 550
C thermal stability in
comparison to neat PS
PEEK/LCP 99/1, 98/2, 95/5, e Melt mixing at 370
C, TGA in N2, 10
C/min, Increase of degradation [63]
90/10, 85/15, 50 rpm from 50 to rate in the blend if
70/30, 50/50, 700
C compared to pure
30/70, 15/85 polymers
POM/EMA 1, 3, 5 wt% e Injection molding, 230- TGA in O2,from 30 to POM/SBS blends having [64]
POM/SBS 225-220-215
C 400
C at 20
C/min; lower thermooxidative
thermooxidative ageing stability than POM/EMA
in oven at 140
C for 111
days
PU/CSM 50/50 e internal mixer at a TGA in air, 10
C/min, Thermal stability deeply [65]
PU/EPH constant shear rate from 25 to 600
C affected by the blending
PU/CR and25
C; blends then technique; masterbatch
allowed to cure in a hot technique lead to
press at 150
C degradation at lower
temps
LDPE/TMBS 50/50 e melt thermo-oxidative thermo-oxidative [66]
HDPE/TMBS mixing þ compression treatment in oven at treatment decreased the
molding 100
C, 360 h, in air activation energy of the
thermal decomposition of
both components in the
blends, but mainly
modified the thermal
properties of starch
during subsequent
degradation process in
soil

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Table 1 (continued )

Polymers Blend composition Compatibilizers/ Processing Degradation conditions Degradation outcomes Ref.
Additives

PTMC/PLA 80/20, 50/50, Melt mixing in a sample TGA in N2, at 2-5-10-20- PCL favored the thermal [67]
PTMC/PCL 20/80 wt/wt pan 40
C/min, from 50 to degradation of PTMC,
600
C while PLA enhanced
thermal stability; each
biodegradable polymer
led to completely
different modifications of
the thermal degradation
paths of the less stable
PTMC
PBAT/TPS 10%, 20%, and 30% Commercial chain Laboratory internal mixer Laboratory internal mixer TPS content favors [68]
starch (by weight) extender (oligomer with fitted with high intensity fitted with high intensity thermal degradation in
epoxy and methacrylate rotors, 60 rpm, 15 min, rotors, 60 rpm, 15 min, the blends
residues) 140/170/200
C 140/170/200
C
Nylon6/PP 80/20 wt/wt Laboratory mixer Processing in laboratory Thermolability of PP-g- [69]
Nylon6/PP-g-MA mixer, 240
C, 60 rpm, AA leads to a decrease of
Nylon6/PP-g-AA different mixing times the compatibilization
efficiency; worse
properties in comparison
to PP-g-MA blends
PLA/PBAT 75/25 wt/wt Batch mixer Processing in batch Conditions causing higher [70]
mixer, air and nitrogen PLA degradation lead also
atmosphere, 150e200
C, to higher copolymer
50 rpm, mixing time formation and thus better
10 min dispersion and ductility
PP/EOC 90/10, 80/20 wt/wt Mixing at 50 rpm and Single screw extruder, air Degradation mechanisms [71]
200
C, then extrusion atmosphere, up to 6 mainly based on PP chain
cycles scission without
oxidation; EOC mitigated
the reduction of ductility
upon recycling
LDPE/PA6 75/25 wt/wt Melt processing in a Reprocessing in a single- Degradation significant at [72]
corotating twin-screw screw extruder(180 higher processing times
extruder e240
C, 60 rpm) or batch and involving branching
mixer (240
C, 1 h, 30/ and crosslinking
60 rpm) phenomena

comparable to those of the ABR blends; on the other hand, the ENR
blends with PVC showed to be more prone to oxidative aging, and
this was attributed to the susceptibility of the oxirane group to
ring-opening reactions, particularly in presence of the HCl pro-
duced by PVC during its degradation. They also found that the
amine-type antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline
could mitigate the thermo-oxidative aging, while calcium stearate
was effective in stabilizing only the PVC/NBR blend.
Thaumaturgo et al. [47] investigated the thermal stability of
PVC/EVA blends. EVA samples with different vinyl acetate content
were used. It was found that all of the blends showed autocatalytic
effects, thus increasing the degradability; however, blends with
EVA with higher vinyl acetate contents also showed a reduced
degradability in comparison to those with lower VA-containing
EVAs.
Mohamed et al. [48] investigated the thermal degradation
behavior of PVC-poly(vinyl butyral) (PVB) blends. The blends were
prepared by solution blending and their degradation behavior was
mainly investigated by thermogravimetric method. The thermal
stability was found to increase upon increasing the PVB percentage.
Fig. 1. Interaction between the degradation products from PVC and PMMA, leading to
a stabilization of PVC. Reprinted from Ref. [50], Copyright (2007), with permission
from Elsevier.
Zulfiqar et al. [49] studied the thermal degradation of blends of
PVC with polydiphenylsiloxane (PDPS) and poly-
dimethyldiphenylsiloxane (PDMDPS), by thermogravimetric
method, which also allowed calculating the activation energy and
order of reactions for the blends and the component polymers.
They found that low amounts of the two polysiloxanes led to slight
destabilizing effects, while with contents higher than 50%, a sta-
bilizing effect was detected and this increased upon increasing the
siloxane content; this was especially true for the PDMDPS blends.
They explained this result considering that a) being polysiloxanes
more stable than PVC, an increase in their percentage would
obviously increase the stability, b) the increasing amount of
siloxane also leads to an accumulation of HCl or Cl radicals, thus
decreasing the catalyzing effect and the rate of
dehydrochlorination.
Ahmad et al. [50] studied the thermal degradation of PVC/
PMMA blends. It was found that the thermal decomposition tem-
peratures of PVC in presence of PMMA were higher than in the neat
PVC; in particular, the stabilizing effect was found more significant
with 10 wt% PMMA content. This was interpreted considering the
following reaction mechanism between the degradation products
coming from both of the polymers, leading to a stabilization of PVC
(see Fig. 1).
Pielichowski [51] studied the thermal degradation of poly-
vinylchloride/polyaniline (PVC/PANI) electrically conductive
blends. Once more, it was found that the main decomposition
product from PVC degradation, i.e. HCl, has a primary role in pro-
moting the decomposition of the second component of the blend;
in this case, reacting with PANI structures, characterized by
different protonation degree.

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Fig. 2. Ester-amide interchange reaction. Reprinted from Ref. [52], Copyright (1998), with permission from Elsevier.
Few studies focused on polyamide/rubber blends. In details, Jha
and Bhowmick [52] studied the thermal degradation behavior of
blends of nylon-6 and an acrylate rubber (ACM) by thermogravi-
metric method. It was found that the thermal stability of the blend
was lower than that of nylon-6, and an ester-amide interchange
reaction at high temperatures, preferentially degrading the poly-
amide phase, was postulated in order to explain this behavior. This
interchange reaction was schematized as reported in Fig. 2.
Choudhury et al. [53] investigated the thermal degradation
behavior of nylon 66/maleic anhydride grafted ethylene propylene
rubber (EPR-g-MA) blends at different EPR-g-MA contents. They
found that the activation energy and the reaction order of thermal
degradation decreased upon increasing the rubber content; this
was partly correlated with the decrease in the dispersed phase
particle size, due to the in situ compatibilization between nylon 66
and EPR-g-MA.
Over the last years, some significant interest has arisen about
PET-PLA blends. This is due to the increasing presence of PLA res-
idues in post-consumer PET, easily explainable considering the
growing use of PLA, in replacement for PET, for the manufacturing
of beverage bottles [54]. This obviously leads to increased concern
for the thermal degradation behavior of PET/PLA blends.
Acar et al. [55] studied the thermal-oxidative degradation
behavior (mainly, the degradation kinetics) of PET modified with
PLA, i.e. a PET-co-PLA copolymer prepared via solution technique.
The incorporation of PLA resulted in a higher degradation rates
upon increasing the PLA amount. On the other hand, the degra-
dation activation energies decreased upon increasing PLA content.
McLauchlin and Ghita [56] investigated the thermal and me-
chanical behavior of PLA-PET blends. It was found that, while
amounts of PLA up to 2% marginally decreased the onset of rapid
degradation, the presence of 5% (or higher) PLA amount signifi-
cantly reduced the onset temperature of degradation. This was
partly attributed to PLA containing a higher weight proportion of
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embodied oxygen.
The scientific literature reports also several other studies
regarding specific pairs of polymers in a blend. Some of them are
briefly described in the following.
Chaudry et al. [57] studied the effects of processing conditions
on the properties of PC/ABS blends upon changing mixing tem-
perature, speed and time, and the morphology after an annealing
treatment at 250
C in nitrogen. Torque measurements pointed out
significant degradation at higher temperatures. This was attributed
to the presence of residues from the synthesis of ABS, which pro-
moted chain scission on PC. Annealing led to modifications of the
phase morphology, i.e. shrinking and coalescence of PC and ABS
phases under heating; upon increasing the annealing time, the PC
domains became larger.
Chiantore et al. [58] investigated the thermal oxidative degra-
dation of an AES blend, formed by a mixture of ethylene-propylene-
diene (EPDM) rubber, styrene-acrylonitrile (SAN) copolymer and
SAN grafted on EPDM chains. They found that the oxidation re-
actions start on the EPDM chains at temperatures lower than those
expected for the formation of volatile compounds, with a mecha-
nism typical of hydrocarbon oxidation. The graft polymer showed
relatively high reactivity; during the oxidation, crosslinking
occurred simultaneously with chain scission and partial destruc-
tion of the graft structure.
Grguric et al. [59] studied the thermal-oxidative degradation of
high impact polystyrene (HIPS)/styrene-butadiene-styrene (SBS)
blends. It was found that the degradation rate, as well as the kinetic
constant, increases on increasing the content of the SBS phase.
Jansen and Soares [60] investigated the effect of compatibilizers,
blend composition and curing process on the thermal degradation
of natural rubber (NR)/EVA blends. In particular, they studied the
effect of the presence of poly(ethylene-co-vinylalcohol-co-
vinylmercaptoacetate) (EVASH) as compatibilizer, with the addi-
tion of dicumylperoxide (DCP) as curing agent. Degradation was
 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14
studied by thermogravimetric method, as well as by size exclusion
chromatography (SEC) for determination of the molecular weight
changes. It was found that the EVASH significantly contributed in
delaying the loss of mechanical resistance due to the aging (after
leading to an increase of the ultimate tensile strength after one day
of exposure at 70
C); they demonstrated that the decrease of the
molecular weight with aging time was slowed down in presence of
EVASH.
Ganesh et al. [61] investigated on the stabilization of thermal
degradation of poly(methyl methacrylate) (PMMA) by polysulfide
polymers (i.e. poly(styrene disulfide), PSD, and poly(styrene tetra-
sulfide), PST). Both PSD and PST were found to have a stabilizing
effect on the blend, up to 300
C; this was explained considering
the chain transfer reaction of macroradicals coming from PMMA to
the sulphur-sulphur bond, and the radical recombination reaction
of PMMA-derived macroradicals with thiyl radicals coming from
PSD and PST.
Yao and Wilkie [62] studied the thermal degradation of blends
of PS and poly(sodium 4-styrenesulfonate), PSSNa, as well as the
copolymer poly(styrene-co-sodium 4-styrenesulfonate). They
showed that the thermal degradation of the blends occurs in two
independent steps; when the amount of PSSNa is relatively low, the
inhibition of the PS degradation is only moderate; when higher
amounts are used, there is an increased formation of char, which
helps in providing thermal protection. However it was observed
that, in general, this is likely to significantly happen only when the
degradation temperature of the polymer to be protected is close to
the relatively high degradation temperature of PSSNa.
Naffakh et al. [63] studied the thermal decomposition of blends
of poly(aryl ether ether ketone), PEEK and a thermotropic liquid
crystalline polymer (LCP). They found that thermal stability was
significantly accelerated by blending; more in detail, they showed
that the degradation mechanisms of the neat polymers were the
same as components of the blend, therefore the above mentioned
thermal degradation behavior was mainly linked to an increased
degradation rate, rather than a modified mechanism.
Wang [64] studied the thermal stability of polyoxymethylene
(POM) and its blends with poly(ethylene-methylacrylate) (EMA)
and poly(styrene-butadiene-styrene) (SBS). In particular, the effects
of thermooxidative aging in oven at 140
C for 111 days were
evaluated. First of all, it was observed that POM undergoes
continuous degradation during the thermooxidative aging in oven.
The blends showed similar degradation patterns (with the chain
scission of POM chain playing the main role) but SBS lead to higher
degradation rates in comparison to EMA; the degradation of POM/
SBS occurred mainly in the amorphous phase, while both in the
amorphous and the crystalline phase for POM/EMA blends.
Khatua and Das [65] studied the thermal stability of 50/50
blends of polyurethane (PU) with three different elastomers,
namely chlorosulfonated polyethylene (CSM), epichlorohydrin
(EPH) and polychloroprene (CR). They adopted different blending
techniques, finding that blending via masterbatch technique
degraded at a lower temperature, maybe because of the formation
of inter-chain crosslinks due to the reactive functional groups of the
elastomers and to the blending before the addition of curing agents.
The scientific literature also reports on specific studies about
thermal/thermomechanical degradation of blends containing
starch and/or other biodegradable polymers.
Blasco et al. [66] performed studies on polyethylene blends with
a biodegradable masterbatch containing starch (MBS), subjected to
thermo-oxidative treatment and then to a soil burial test. More in
details, LDPE/MBS and HDPE/MBS blends were prepared by melt
mixing and subsequent compression molding, and then subjected
to a thermo-oxidative treatment, prior to soil burial tests. They
observed that the thermo-oxidative treatment influenced mainly
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the morphological and thermal properties of PE in both of the
blends (in particular, the crystallinity); however, it also affected the
subsequent soil burial degradation behavior, mainly by changing
the morphological and thermal behavior of the starch.
Marquez et al. [67] studied the thermal degradation of blends
containing poly(trimethylene carbonate) (PTMC) with either pol-
ylactide or polycaprolactone. They found out that the degradation
behavior of PTMC significantly changes upon mixing with PLA or
PCL; in particular, the degradation behavior of each blend was
peculiar, and did not correspond to just a superposition of the
degradation processes of each component. Thermal decomposition
of either PCL or PLA was increased upon mixing with PTMC, which
thus acted as a degradation promoter, because of its lower thermal
stability. On the other hand, adding PCL or PLA to PTMC lead to
completely different results: PLA modified the degradation paths of
PTMC, leading to a stabilizing effect while PCL promoted the
degradation of PTMC; more in details, the usually secondary
decomposition process associated with an unzipping depolymer-
ization reaction at lower temperatures was favored in presence of
PCL, while PLA practically inhibited this stage and, on the other
hand, favored typical random chain scissions, with a main degra-
dation path characterized by higher activation energy and occur-
ring at higher temperatures.
Marinho et al. [68] recently investigated the degradation, during
processing conditions, of poly(butylene adipate-co-terephthalate)/
thermoplastic starch (PBAT/TPS) blends. More specifically, PBAT/
TPS blends were processed at different temperatures and the effect
of a chain extender was also evaluated. The Authors used the torque
change rate during processing to monitor the molar mass variations
due to degradation. They found that TPS promoted the thermal
degradation of the blends, in comparison to the pure components.
The process was significantly dependent on temperature and
composition (degradation rate change increasing upon increasing
temperature and TPS content). The presence of 1% chain extender
allowed a partial recovery of the degradation, especially at higher
processing temperatures.
La Mantia and Mongiovì [69] investigated the degradation of
compatibilized and uncompatibilized Nylon6-polypropylene
blends. The thermomechanical degradation was performed by
processing the blends in a laboratory internal mixer, with different
processing times, of Nylon6/PP blends, as well as the same blends
but containing PP-g-MA or PP-g-AA (polypropylene functionalized
with acrylic acid) in replacement for PP. They found that two
mutually influencing processes, i.e. modification of the compati-
bility and degradation, occur during the processing. In Nylon6/PP-
g-AA blends the compatibilizing effect decreases as the mixing
time increases; in Nylon6/PP-g-MA ones, the good thermal stability
of leads to blends with a relatively good thermomechanical resis-
tance; uncompatibilized blends, on the other hand, show good
properties during the first stage of processing due to the formation
of Ny-g-PP copolymers, but the properties decrease upon
increasing the mixing time, due to reduction of the molecular
weight.
Signori et al. [70] studied the thermal degradation of PLA/PBAT
blends upon melt processing, in particular the effects on the mo-
lecular weight distribution, morphology, and thermo-mechanical
properties. It was found that the most important factor is the for-
mation of PLAePBAT copolymers. In particular, conditions favoring
the formation of high copolymer amounts improved the dispersion
of PBAT into the PLA matrix as well as the ductility. These condi-
tions were found to be those with higher degradation effects on PLA
(for instance, higher temperatures). On the other hand, less PLA
degradation lead to reduced copolymer formation and thus poorer
dispersion of PBAT into the PLA matrix, thus providing higher
moduli.
8 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14

Table 2
Synoptic table on photooxidation of several polymer blends.

Polymers Blend composition Compatibilizers/ Processing Degradation conditions Degradation outcomes Ref.
additives

PVC/PVAc 100/1; 100/5; 100/10 e Solution casting UV-irradiation with PVAc decelerates PVC [73]
phr low pressure mercury photodegradation,photocrosslinking
vapor lamps and photooxidation leading to
(l ¼ 254 nm; carbonyl groups formation.
I ¼ 2.35 mW/cm2) at
room temperature in
air.
Exposure period: up to
25 h
PVC/PVA 80/20; 60/40; 40/60; e Solution casting UV-irradiation with The PVC/PVA blends are characterized [74]
20/80 wt% low pressure mercury by higher photostability comparing to
vapor lamps pure PVC but they were less
(l ¼ 254 nm; photostable than PVA.
I ¼ 34.3 W/m2) at room The photodecomposition of PVC/PVA
temperature in air. blends depends on their composition as
Exposure period: up to well as on interactions between
6h components and products of their
degradation.
PVC/MBS 100/1; 100/3; 100/6; e Melt compounding UV-irradiation with MBS restrains PVC [75]
100/9; 100/12; phr with a roller mill at fluorescent lamps photodehydrochlorination but
150
C for 5 min. (l ¼ 254 nm; accelerates its photooxidation.
Samples obtained by I ¼ 1.12 mW/cm2) at
compression molding 30
C in air.
at 135
C. Exposure period: up to
10 h
PCL/PVC 50/50 wt% e Solution casting UV-irradiation with Blend gave lower CO2 emission than [76]
xenon lamps filtered either of the two homopolymers,
with water indicating that the
(l > 275 nm) in oxygen. interaction of the two components in
Exposure period: up to the blend provided a beneficial
3h reduction of photodegradation.
PVC/PMMA 80/20; 60/40; 50/50; e Solution casting UV-irradiation with The efficiency of the photooxidation [77]
40/60; 20/80 wt% low pressure mercury reactions increased with increasing PVC
vapor lamps content and these reactions occurred
(l ¼ 254 nm; approximately in accordance with the
I ¼ 19.9 W/m2) in air. additivity rule.
Exposure period: up to The presence of chlorine radicals from
12 h PVC modifies the route of PMMA
photochemical processes in PVC/PMMA
blends
PS/PVAc 95/5; 90/10; 80/20; 50/ e Solution casting UV-irradiation with Photooxidation and photodegradation [78]
50; 20/80; 10/90; 5/ polychromatic light by are accelerated in blends compared to
95 wt% high pressure mercury pure PS and PVAc. The accelerating
lamps (l ¼ 248 effect is caused by mutual interactions
e578 nm; I ¼ 32 mW/ of small degradation fragments or free
cm2) in air at room radicals which can migrate to a phase of
temperature. the second polymer and reinitiate
Exposure period: up to degradation.
4h
PS/PVAc 95/5; 90/10; 80/20; 50/ e Solution casting UV-irradiation with The degradation processes are more [79]
50; 20/80; 10/90; 5/ fluorescent UVB lamps efficient in PS/PVAc blends than in pure
95 wt% (l ¼ 280e350 nm with polymers. The photooxidation depends
a maximum peak at strongly on sample composition. i.e. it is
313 nm; I ¼ 1.67 mW/ accelerated for blends with 5e50% of
cm2) in air at room PVAc and is retarded in a sample
temperature. containing >50% of PVAc.
Exposure period: up to
100 h
PS/HIPS 50/50 wt% Acetophenone Melt compounding UV-irradiation with The photodegradability of the blend [90]
(2.5 and 5%); with modular filtered xenon lamps increases with increasing the ketone
benzophenone intermeshing (l > 300 nm; I ¼ 60 W/ amount. Moreover, benzophenone
(2.5 and 5%) corotating m2). induces higher changes in the chemical
twin-screw extruder at Exposure period: up to structure and molecular weight.
210
C. 12 h
Samples obtained by
compression molding
at 200
C.
PVME/PS 80/20; 50/50; 30/ e Solution casting UV-irradiation with PVME photooxidation is the main cause [80]
70 mol% medium-pressure of the degradation of the blends.
mercury sources Moreover, PVME influences the
filtered with a photooxidation of PS and vice versa.
borosilicate
(l > 300 nm) at 60
C in

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 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14 9

Table 2 (continued )

Polymers Blend composition Compatibilizers/ Processing Degradation conditions Degradation outcomes Ref.
additives

air.
Exposure period: up to
200 h
PP/PS 85/15; 70/30; 55/45 wt SBS (1 and 3 phr) Melt compounding UV-irradiation with The photodegradation of the PP/PS [81]
% with a single screw low pressure mercury blends occurs
extruder (180e230
C). vapor lamps faster and with a larger carbonyl
Samples obtained by (l ¼ 254 nm; I ¼ 4 mW/ formation than the homopolymers. The
compression molding cm2) in air at room kinetics of carbonyl formation of the
at 200
C. temperature. blends was a function of PP content. The
Exposure period: up to carbonyl formation rate increases with
30 h increasing SBS amount.
PP/HIPS 90/10; 80/20; 70/30 wt SBS (10 wt%) Melt compounding Artificial weathering The blends exhibit a higher [82]
% with a twin screw with fluorescent UV photostability in comparison with the
extruder (180e200
C). lamps (l > 290 nm; pure polymers. This increase of
Samples obtained by I ¼ 0.89 W/m2) in air. photostability was even greater when
injection molding. Exposure period: cycles SBS was added to the blends.
of 8 h of UV light at
60
C followed by 4 h of
condensation at 50
C
(up to 2520 h)
PP/PA-6 70/30 wt % PP-g-MA (2 wt %) Melt compounding Artificial weathering The degradation rate of the [84]
with a counter rotating with xenon lamps uncompatibilized blends is higher than
twin screw extruder at (l > 300 nm; I ¼ 90 W/ that of both homopolymers at long
240
C. m2) in air at 45
C. exposure times. The addition of PP-g-
Samples obtained by Exposure period: up to MA increases slightly their
compression molding 250 h photooxidation rate.
at 240
C.
PP/PBT 70/30; 50/50; 30/70; wt GMA Melt compounding. UV-irradiation with The pure photolytic reactions are [83]
% Samples obtained by medium-pressure restricted to the PBT component.
compression molding mercury sources The photooxidative degradation of the
at 240
C. filtered with a various blends involves a pure
borosilicate photolytic degradation and a photo-
(l > 300 nm) at 60
C induced oxidation of PBT sequences.
both in air and under
vacuum.
Exposure period: up to
70 h
PEC/PVA 70/30; 50/50; 30/70; wt e Solution casting Artificial weathering PEC/PVA blends exhibited the improved [89]
% with xenon lamps resistance to weathering comparing
(l ¼ 290 nm; with both polymers aged individually.
I ¼ 250 W/m2) in air at
35
C.
Exposure period: 39
ageing cycles of 10 h of
UV light followed by
10-h dark period (up to
780 h)
PEC/PEO 1:2; 1:1; 2:1 weight- e Solution casting UV-irradiation with The susceptibility of the blends to UV [88]
ratio low pressure mercury radiation
vapor lamps depends on the ratio of components. In
(l ¼ 254 nm; particular, the most sensitive to UV-
I ¼ 34.3 W/m2) at room irradiation is the blend PEC/PEO at
temperature in air. equal weight-ratio (1:1)
Exposure period: up to
20 h
LDPE/PA-6 75/25; 50/50; 25/75; wt e Melt mixing at 240
C. Artificial weathering The photooxidation rate of the blends is [85]
% Samples obtained by with fluorescent UV higher than that of the homopolymers.
compression molding lamps (l > 300 nm) in The photooxidation starts in the
at 240
C. air. polyamide phase, and the polyamide
Exposure period: cycles radicals promote the degradation in the
of 8 h of UV light at polyethylene phase.
60
C followed by 4 h of
condensation at 40
C
(up to 120 h)
LLDPE/waste 90/10; 75/25; 50/50; e Melt compounding Artificial weathering The waste phase promotes the [91]
Waste composition: 75/25; 10/90 wt% with a single screw with fluorescent UV photodegradation of the blends.
LLDPE (46%), extruder at three die lamps (l > 300 nm) in
LDPE (51%), head temperatures: air.
HDPE (1%), 175
C; 185
C, 195
C. Exposure period: cycles
PP (2%) wt% Samples obtained by of 8 h of UV light at
film blowing. 60
C followed by 4 h of
condensation at 50
C
(up to 360 h)
(continued on next page)

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10 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14
Table 2 (continued )
Polymers Blend composition Compatibilizers/
additives
LDPE/Cellulose 95/5; 90/10; 85/15; 70/ Aminosilane
30 wt% (1 wt%)
Wang et al. [71] investigated the effects of reprocessing on
blends prepared with polypropylene and ethylene octene copol-
ymer (EOC) blends. The reprocessing of PP leads to a continuous
reduction of the molecular weight, with the expectable effects on
the melt flow index (increasing), the melting and crystallization
temperatures (decreasing) and the crystallinity (increasing). Chain
scission (without oxidation) was involved also in the degradation
phenomena in presence of EOC, which contributed in decreasing
the viscosity and improving the thermal stability. Furthermore, the
first recycling step lead to an increase of the elastic modulus and
the tensile yield stress, while they decreased during the following
reprocessing steps; the elongation at break also decreased, but less
than in the neat PP.
Mistretta et al. [72] studied the thermomechanical degradation
of polyethylene/polyamide6 blend. The blend (75/25 wt/wt) was
prepared in modular corotating twin screw extruder and reproc-
essed in a single-screw extruder and in a batch mixer. It was found
that the thermomechanical degradation of the blend is strongly
dependent on the processing conditions and on the degradation
behavior of each component of the systems, as well as on the
specific interactions between the degradation products of the
components. More in details, the degradation involves both
branching and crosslinking. Indeed, thermomechanical stress dur-
ing multiple extrusions did not cause relevant degradation phe-
nomena; higher processing times in the mixer lead to significant
increase of the viscosity and of the non-Newtonian behavior, due to
the formation of branching and cross-linked structures.
4. Photooxidation
For outdoor applications, it is particularly important to take care
of the resistance of the material to photo-oxidation. Indeed,
exposure of polymers in their normal use conditions leads to
photo-oxidative degradation phenomena, which conversely cause
the general deterioration of their macroscopic properties due to the
variation of molecular weight, chemical structure, and morphology.
The blend composition can significantly affect the
Fig. 3. Simplified mechanism of PVC/PVAc photooxidative degradation. Reprinted from Ref. [73], Copyright (2002), with permission from Elsevier.
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Processing Degradation conditions Degradation outcomes Ref.
Melt compounding UV-irradiation with LDPE/cellulose blends are [86]
with a single screw low pressure mercury less stable than pure components and
extruder with sheet die vapor lamps the photodegradation depends
at 170
C (l ¼ 254 nm; I ¼ 3.5 W/ on blend composition.
m2) in air at room
temperature.
Exposure period: up to
100 h
photodegradative behavior of a polymer blend and can differs from
the behavior of the pure components since, as previously reported,
interactions among the different species in the blends during
degradation and among the degradation products can occur. These
chemical reactions can lead either to an acceleration of the
degradation rate with respect to that of the pure components or to
a stabilizing effect. Moreover, the additive rule cannot often be
applied in case of photostability of polymer blends and, therefore,
the photo-stability of polymer blends is difficult to predict on the
basis of photoresistance of pure components.
Table 2 reports the degradation conditions and the main results
of several works on the photooxidation of polymer blends. Much
attention has been focused on PVC based blends. Indeed, blending
PVC with other polymers can lead to an improvement of its prop-
erties, thus increasing the possible applications. In this regard, the
knowledge of the photo-oxidative behavior of blends containing
PVC is of great commercial importance. Kaczmarek et al. showed
that adding poly(vinyl acetate) to PVC leads to a reduction of its
photodegradation, photocrosslinking and photooxidation [73]. The
authors proposed that this retarding effect due to PVAc can be
attributed to combined reactions between the active species
formed in degraded PVAc (e.g. radicals, peroxides) with the mac-
roradicals and macromolecules in both polymers, as reported in
Fig. 3. Moreover, PVAc can protect PVC photodamage owing to
absorption of harmful UV-radiation by carbonyl groups.
The photostability of PVC has been improved by blending it with
poly(vinyl alcohol) too [74]. Indeed, it was shown that the PVC/PVA
blends were characterized by higher photostability comparing to
pure PVC but they were less photostable than PVA. In particular, in
PVC/PVA blends the amount of carbonyl groups was lower than it
could be predicted on the base of additivity rule, thus indicating
that photooxidation leading to C¼O formation was somewhat
hindered in the blends. In fact, the photodecomposition of PVC/PVA
blends depends on their composition as well as on interactions
between components and products of their degradation.
Chen et al. investigated the influence of methyl methacrylate-
butadiene-styrene copolymer (MBS) on the photostability of PVC/
 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14
MBS blends [75]. They found that MBS restrains the PVC photo-
dehydrochlorination to form polyenes and crosslinking. The
inhibiting effect was attributed to the fact that the Cl radicals
formed by PVC photodehydrochlorination can react with tertiary H
atoms in polystyrene of MBS copolymer and enter the PMMA
chains of MBS copolymer to initiate the depolymerization of MBS.
Nevertheless, it was shown that MBS accelerates the photooxida-
tion of PVC. Indeed, peroxides disintegrate to form carbonyl groups
and hydroxyl groups since the polybutadiene of MBS easily forms
peroxides in the presence of O2. The carbonyl groups in MBS can
cause the photoinitiation of PVC, thus accelerating photooxidation.
Christensen et al. studied the photodegradation of a PCL/PVC
(50/50) blend by following CO2 emission during UV exposure [76].
They showed that the blend gave lower carbon dioxide emissions
than either of the two homopolymers irradiated under the same
conditions, indicating that the interaction of the two components
in the blend provided a beneficial reduction of photodegradation.
They hypothesized that the detailed morphological characteristics
of the blend had a controlling influence over the photo-oxidation.
Kowalonek investigated changes in surface properties of PVC/
PMMA blends upon UV-irradiation [77]. It was found that the ef-
ficiency of the photooxidation reactions increased with increasing
PVC content and these reactions occurred approximately in accor-
dance with the additivity rule. The presence of chlorine radicals
from PVC modified the route of PMMA photochemical processes in
PVC/PMMA blends. In particular, these radicals were able to ab-
stract hydrogen atoms from methyl groups of side substituents or
from methylene groups of main PMMA chains leading to the for-
mation of alkyl radicals resulting in oxidation and chain cleavage.
The author suggested that the degradation process of PMMA, i.e.
chain scissions, took place efficiently in the blends and to a lesser
extent in pure PMMA.
Several studies on the photodegradative behavior of polymer
blends containing polystyrene are reported in the scientific litera-
ture since PS is an excellent polymer suitable for various
applications.
Kaczmarek studied the photooxidative degradation of PS/PVAc
blends at different compositions under UV-irradiation by two
different sources, i.e. a highly energetic, polychromatic light
(l ¼ 248e578 nm) and a fluorescent lamp (emitting light in the
range 280e350 nm with a maximum peak at 313 nm) [78,79]. In
both cases, it was found that photooxidation was accelerated in
blends compared to pure PS and PVAc. The accelerating effect was
caused by mutual interactions of small degradation fragments or
free radicals which can migrate to a phase of the second polymer
Fig. 4. Energy transfer scheme in the photochemical degradation of the blend PP/PS. Reprinted from Ref. [81], Copyright (2007), with permission from Elsevier.
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11
and reinitiate degradation. Moreover, higher efficiencies of photo-
crosslinking, as well as chromophore compounds formation was
observed in all of the blends, in the case of the samples irradiated
by polychromatic light. On the contrary, the photocrosslinking of
PS/PVAc blends irradiated by fluorescent lamps was not observed
during the investigation time. Furthermore, in this latter case the
photooxidation depended strongly on sample composition. i.e. it
was accelerated in blends with 5e50% PVAc and was retarded in a
sample containing >50% of PVAc. On the basis of these results, the
author proved the great influence of light sources on the photo-
oxidative degradation of PS/PVAc blends, showing that poly-
chromatic light with high energy causes more efficient chemical
changes in PS, PVAc and their blends than the less energetic fluo-
rescent light. However, the comparison of results obtained after the
emission of the same dose showed that some processes (mainly,
the degradation) are more efficient when PS/PVAc blends were
irradiated by the fluorescent lamp.
Mailhot et al. investigated the photooxidation of blends of
polystyrene and poly(vinyl methyl ether) [80]. They found that
PVME photooxidation is the main cause of the degradation of the
blends. Moreover, PVME influences the photooxidation of PS and
vice versa. In particular, the analysis of the nature of the photo-
products formed upon irradiation in the blends showed that these
products are similar to those identified in the homopolymers and
no evidence of the presence of photoproducts formed specifically in
the blends was obtained. However, the two components PVME and
PS interacted and the measurement of the oxidation kinetics gave
evidence that the PVME macromolecules are more stable in PS rich
blends and conversely, oxidation of PS macromolecules is enhanced
in PVME rich blends.
Waldman et al. studied the photochemical degradation of PP/PS
blends prepared with different relative proportions of PS and PP,
also using a compatibilizer, the block copolymer of styrene and
butadiene (SBS) [81]. They reported that photodegradation of the
PP/PS blends occurs faster and with a larger carbonyl formation
than in the homopolymers. The kinetics of carbonyl formation of
the blends depended on PP content. The kinetics and mechanism of
UV degradation were explained taking into account the interactions
between the blend components. In particular, the authors hy-
pothesized the energy transfer between the domains as schema-
tized in Fig. 4. PS domains, that form more stable tertiary radicals by
resonance, absorb the UV radiation and interact with the PP do-
mains, that have no significant UV absorption but form more
reactive tertiary carbon radicals. The effect of the interaction be-
tween the domains was enhanced when SBS is used, corroborating
12 F.P. La Mantia et al. / Polymer Degradation and Stability xxx (2017) 1e14
the hypothesis of energy transfer.
On the contrary, Fernandes at al. found that PP/HIPS blends
exhibited a higher photostability in comparison with the pure
polymers [82]. This increase of photostability was even greater
when SBS was added to the blends. They attributed the better
photostability of the blends to the opacity of the materials and to
the larger scattering effect of the interface between the polymers.
The photolysis and the photooxidation of PP/PBT blends have
been investigated by Rivaton et al. [83]. In particular, three different
blends with 30%, 50% and 70% PP were studied and compared with
the behavior of PP and PBT homopolymers. It was found that the
pure photolytic reactions (in the absence of oxygen) were restricted
to the PBT component. The photooxidative degradation of the
various blends was shown to involve a pure photolytic degradation
and a photo-induced oxidation of PBT sequences involving hydro-
peroxidation on the methylene groups in the a position to the ox-
ygen atom of the ester groups. The decomposition of these
hydroperoxides generated hydroxy radicals that could induce the
oxidation of the PP component.
Mouffok et al. investigated the artificial weathering effect on the
structure and properties of PP/PA-6 blends compatibilized with PP-
g-MA [84]. They showed that the photooxidation starts in the PA-6
phase. The degradation rate of the uncompatibilized blends was
higher than that of both the homopolymers at long exposure times.
The addition of PP-g-MA increased slightly their photooxidation
rate. UV exposure increased the crystallinity index and decreased
the melting temperature of PP and PA-6 either as neat homopoly-
mers or as components in the blends.
PA-6 was subjected to artificial weathering blended with LDPE
too [85]. Particular attention was paid to five different compositions
ranging from pure polyethylene to pure polyamide with blends of
LDPE/PA-6 of various compositions: 75/25, 50/50 and 25/75 wt/wt
%. It was found that the photooxidation rate of the blends is higher
than that of the homopolymers. The photooxidation starts in the
polyamide phase, and the polyamide radicals promote the degra-
dation in the polyethylene phase. The rate of polyethylene oxida-
tion was higher in the blends, implying that polyethylene is more
vulnerable to oxidation when blended with PA-6.
Ołdak et al. reported a study on LDPE, cellulose and their blends
with different compositions (5e30% cellulose content) exposed to
UV radiation [86]. They showed that LDPE/cellulose blends are less
stable than pure components and the photodegradation depends
on blend composition. In particular, LDPE blends with a relatively
small amount of cellulose (5e15%) behave differently than mixtures
with a greater content of this natural polymer (30%). The former
samples were characterized by a higher photoresistance, while
samples with 30% cellulose were less stable.
Botta et al. showed that, in LDPE/EVA blends subjected to
accelerated weathering, when the EVA content is increased, the
photostability of the blend improves as well [87]. Indeed, the values
of the photo-oxidation induction time and of the half time increase
upon increasing the EVA content in LDPE/EVA blends. The me-
chanical results were confirmed by the FTIR analyses, showing that
the increase of the carbonyl index is larger on increasing the LDPE
content in LDPE/EVA blend films.
Kaczmarek et al. studied the photodegradation behavior of
biodegradable blends based on pectin (PEC) and poly(ethylene
oxide) at different weight-ratios obtained by physical mixing in
aqueous solutions and evaporation of the solvent [88]. They found
that the susceptibility of the blends to UV radiation depends on the
components ratio. In particular, the blend of PEC/PEO at equal
weight-ratio (1:1) was found to be particularly susceptible to the
destructive effect of UV radiation.
On the contrary, PEC blended with PVA and subjected to
accelerated weathering, exhibited an improved resistance to
Please cite this article in press as: F.P. La Mantia, et al., Degradation of polymer blends: A brief review, Polymer Degradation and Stability (2017),
http://dx.doi.org/10.1016/j.polymdegradstab.2017.07.011
photodegradation compared with both of the polymers aged
separately [89]. Mutual stabilization effect was explained by
intermolecular interactions between PEC and PVA as confirmed by
spectroscopic methods.
5. Conclusions
Predicting the degradation behavior of a polymer blend on the
basis of the properties of pure components is, as a rule, very diffi-
cult. Indeed, the blend composition, as well as the possible pres-
ence of a compatibilizer, can strongly affect the degradation
behavior of a polymer blend and can differ from the degradation
routes of the pure components since interactions among the
different species in the blends during degradation and among the
degradation products can occur. Therefore, the additive rule cannot
be often applied in case of degradation of polymer blends, since the
degradation rate of a polymer blend can result higher, intermediate
or lower than that of the pure components.
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Please cite this article in press as: F.P. La Mantia, et al., Degradation of polymer blends: A brief review, Polymer Degradation and Stability (2017),
http://dx.doi.org/10.1016/j.polymdegradstab.2017.07.011