Polymer Testing 47 (2015) 130e136

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material behaviour

Impact of fullerenes on the thermal stability of melt processed

polystyrene and poly(methyl methacrylate) composites
Paulo Pereira, Hugo Gaspar, Liliana Fernandes, Gabriel Bernardo*
~es, Portugal
Institute for Polymers and Composites/I3N, University of Minho, 4800-058 Guimara

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

Article history: The impact of the two fullerenes C60 and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) on the
Received 28 July 2015 thermal and thermo-oxidative stability of the corresponding melt processed composites with the two
Accepted 2 September 2015 polymers polystyrene (PS) and poly(methyl methacrylate) (PMMA), was studied using both dynamic and
Available online 4 September 2015
isothermal thermogravimetric analysis (TGA). For each polymer, three different composites with C60
loadings of 1.0 wt% and 3.0 wt% and PCBM loadings of 1.0 wt% were considered. The aim of this work was
Keywords:
to compare the stabilization effect of both fullerenes on PS and PMMA. The results obtained show un-
Polystyrene
equivocally that, although PCBM has lower thermal and thermo-oxidative stability than C60, the PS-PCBM
Poly(methyl methacrylate)
C60
and PMMA-PCBM composites have higher thermal and thermo-oxidative stability than the corre-
PCBM sponding PS-C60 and PMMA-C60 composites. These results corroborate our previous reports, on showing
Fullerenes that PCBM is better than C60 at improving the thermal and thermo-oxidative stability of polymers which
Thermal stability degrade through radical degradation mechanisms.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
In the last few decades, a large number of studies have been
performed aimed at improving the thermal and thermo-oxidative
stability of polystyrene (PS) and poly(methyl methacrylate)
(PMMA) by compounding them with different micro- and nano-
particles as well as with chemical antioxidants. Amongst the par-
ticles considered are: clays (montmorillonite, etc) [1e14], layered
double hydroxides (LDHs) [15e18], cadmium sulfide [19],
aluminum hypophosphite [20], silica [21e25], polysilsesquioxanes
[26], calcium carbonate [27], alumina oxides [28,29], antimony
oxide [30], iron oxide [10,31], titanium oxide [10,31,32], zinc oxide
[29,33], magnesium dihydroxide [34], silver [35], titania [36], zir-
conia [37], phenolic phosphite antioxidants [38], photoinitiators
[39], graphite [40,41], carbon nanotubes [42] and the fullerenes C60
[43e52] and PCBM [46,52].
Troitskii et al. [43] observed that the addition of 0.04 mol% of C60
to PS caused an increase of ca. 30 min in the induction period that
precedes the beginning of mass loss under an oxygen atmosphere
at 238
C. Zeinalov et al. [44] observed that the addition of 1% wt of
C60 to PS increased the thermo-oxidative stability of PS from
* Corresponding author.
E-mail address: gabriel.bernardo@dep.uminho.pt (G. Bernardo).
>270
C to > 300
C. Kim et al. [45] prepared C60/PS nanoparticles
by emulsion polymerization which also showed increased thermal
stability when compared to the pristine PS.
The addition of small quantities of C60 (0.2 mol%) to PMMA
was also shown by Troitskii et al. [43,47] to retard considerably the
polymer's thermal degradation both in vacuum [47] and in the
presence of oxygen [43]. The authors attributed this effect to the
interaction of C60 with macro-radicals, which are generated in the
thermal degradation of PMMA, with formation of less reactive
species. An increase in the thermo-oxidation stability of PMMA
upon addition of 1 and 10 wt% C60 has also been reported by
Ginzburg et al. [48]. Zhogova et al. [49] found that C60 increases the
temperature of thermal degradation of PMMA when exposed to
ionizing radiation. Zuev at al [50] have also reported on the stabi-
lizing effect of C60, in concentration of ca. 1 wt%, responsible for
increasing the thermal stability of acrylic polymers. According to
these authors, the addition of C60 hinders the random scission re-
actions of the main chain which occur through a radical pathway,
but does not influence the non-radical reactions in the side chains,
which occur at higher temperatures. Similar observations were
made more recently by Zhao et al. [51] in the study of PMMA
composites containing 1 and 2 wt% loadings of C60.
C60 has also been shown to increase the thermal stability of
other polymers such as polyethylenes [51,53,54], high-density
polyethylene (HDPE)/ethylene vinyl-acetate copolymer (EVA) [55]

http://dx.doi.org/10.1016/j.polymertesting.2015.09.004
0142-9418/© 2015 Elsevier Ltd. All rights reserved.
 P. Pereira et al. / Polymer Testing 47 (2015) 130e136
and polypropylene (PP) [51].
The fullerene derivative [6,6]-phenyl-C61-butyric acid methyl
ester (PCBM) is widely used as an electron acceptor in polymer
photovoltaic applications [56]. Our group has previously shown
that PCBM, when blended with some p-conjugated polymers
commonly used in organic electronics, can increase their thermo-
oxidation stability at high temperatures [57,58]. Furthermore, and
despite the fact that the fullerene PCBM has a lower thermal and
thermo-oxidation stability than the unfunctionalized C60, our
group has recently reported for the first time in the literature that
PCBM, when blended with some commodity thermoplastics (such
as polystyrene [46], poly(methyl methacrylate) [52] and poly-
ethylene [54]), can impart to the corresponding composites a
higher thermal and thermo-oxidative stability than the unfunc-
tionalized and chemically more stable C60. This apparent contra-
diction stems, most likely, from the fact that PCBM disperses better
in the corresponding polymer matrices due to its organic ligand.
In our two previous studies with PS [46] and PMMA [52], the
composites were prepared using solution blending followed by
precipitation in a non-solvent, and the minimum fullerene loadings
considered were 5 wt%. However, in the commodity plastics in-
dustry, melt processing is the ubiquitous technique for mixing and
forming of polymers and polymer composites. Furthermore, the
still high prices associated with the fullerene nanoparticles make
the large scale production of thermoplastic composites containing
fullerene loadings as high as 5 wt% economically unfeasible.
Therefore, at least from a practical perspective, there is obvious
interest in exploring the impact of very small amounts (~1 wt%
loadings) of these fullerenes (C60 and PCBM) on the thermal and
thermo-oxidative stability of melt processed PS and PMMA
composites.
In the present work, we conduct a comparative study on the
impact of the two fullerenes C60 and PCBM, on the thermal and
thermo-oxidative stability of the corresponding PS and PMMA
composites, prepared by melt extrusion. Two different fullerene
loadings were considered, namely 1.0 wt% (C60 and PCBM) and
3.0 wt% (only C60). Our goal is to understand how the functionali-
zation of the fullerenes affects the thermal and thermo-oxidative
stability of the corresponding PS and PMMA composites.
2. Experimental section
2.1. Materials
The two polymers considered in this work were: (a) polystyrene
from Sigma Aldrich (catalog # 430102) with average Mw~192.000
and MFI ¼ 6.0e9.0 g/10 min (200
C/5 kg) and (b) poly(methyl
methacrylate), Plexiglas 7H extrusion grade, with MFI ¼ 1.4 cm3/
10 min (230
C, 3.8 kg, ISO 1133).
The two fullerenes considered in this work were: a) C60 (>99.5%
purity, Solenne BV, Mw ¼ 720.64 g mol1) and b) phenyl-C61-
butyric acid methyl ester (PCBM) (>99% purity, Solenne BV,
(a) (b)
Fig. 1. Chemical structures of: (a) C60; (b) PCBM; (c) Polystyrene (PS) and (d) Poly(methyl methacrylate) (PMMA).
131
Table 1
Experimental conditions during melt compounding in a twin-screw extruder. T1 to
T4 are the temperatures along the extruder, being T1 the temperature in the region
closer to the hopper and T4 the temperature in the region closer to the die.
Polymer Temperatures Screw velocity (rpm) Feeding screw velocity (rpm)
PS T1 ¼ 135 71 20
T2 ¼ 190
T3 ¼ 200
T4 ¼ 210
Tdie ¼ 220
PMMA T1 ¼ 135 71 20
T2 ¼ 200
T3 ¼ 215
T4 ¼ 230
Tdie ¼ 245
Mw ¼ 910.88 g mol1). The chemical structures of all the materials
(polymers and fullerenes) used in this work are shown in Fig. 1.
2.2. Experimental procedure
PS and PMMA were melt compounded with C60 and PCBM in a
Microlab Twin Screw extruder from Rondol, using the experimental
conditions indicated in Table 1. In this preparation step, appropriate
amounts of each polymer and each fullerene were mixed in powder
form and then fed into the twin-screw extruder. The extruded fiber
samples were then stored for subsequent characterization.
PS and PMMA nanocomposites were prepared containing 1.0 wt
% and 3.0 wt% of C60 and 1.0 wt% of PCBM.
Thermogravimetric analysis (TGA) was carried out using a TA
Q500 thermobalance. The instrument was calibrated with respect
to indium and aluminum standards. Extruded samples (~5 mg)
were placed in platinum crucibles and dynamic tests were per-
formed by heating the samples from 40
C to 600
C using a ramp of
10
C min1, under nitrogen and air flow at 50 mL min1. Isothermal
tests of the extruded pure polymers as well as of the 1.0 wt% C60 and
1.0 wt% PCBM composites were also performed for 1 h under ni-
trogen and air flow at several different temperatures.
3. Results and discussion
3.1. Thermal stability of PS/fullerene nanocomposites (N2
atmosphere)
Fig. 2 shows the thermogravimetry (TG) and the derivative
thermogravimetry (DTG) results (inset) for the pure PS, and for the
as-prepared melt compounded PS:C60 and PS:PCBM composites, as
a function of temperature under nitrogen.
The thermal degradation of PS and of all the PS-fullerene com-
posites, occurs in a single step, as evidenced by the single peak
observed in the corresponding DTG curves. This degradation be-
gins, for all the composites, at ca. 340
C and is slow until ca. 380
C.
(c) (d)
132 P. Pereira et al. / Polymer Testing 47 (2015) 130e136

Fig. 2. Total mass percentage and derivative thermogravimetry (inset) obtained from
Fig. 3. Isothermal thermogravimetry, for 60 min, at 350
C of the PS pure (black) and
TGA of PS/fullerene nanocomposites under N2 atmosphere. 1C60, 3C60 and 1PCBM
the composites PSþ1%C60 (red) and PS þ 1%PCBM (blue), in nitrogen atmosphere. (For
correspond respectively to the composites with 1.0 wt% C60, 3.0 wt% C60 and 1.0 wt%
interpretation of the references to color in this figure legend, the reader is referred to
PCBM.
the web version of this article.)

Then, from ca. 380
C until ca. 450
C it shows a very fast and
extensive mass loss, and at 450
C it has degraded almost
completely leaving no residue, apart from the fullerene residues
which persist until the end of the experiments at 600
C. It is
appropriate to emphasize that, in previous work [46,52], similar
dynamic thermogravimetry tests of pure C60 and pure PCBM under
nitrogen flow have shown that the total residual mass of C60 at
600
C was as high as ~97 wt% and that of pure PCBM at 600
C was
as high as ~90 wt%.
The main results obtained for the different PS composites are
summarized in Table 2, namely the temperatures at which 2 wt%,
5 wt%, 10 wt% and 50 wt% of mass loss occurs as well as the tem-
peratures at which the volatilization rate attains its maximum
value (Tmax) which correspond to the peak maxima in the DTG
curves. Also indicated in Table 2 are the corresponding variations in
thermal stability of each composite compared with the pure poly-
mer (DT2%, DT5%, DT10%, DT50% and DTmax).
As shown in Fig. 2 and Table 2, under N2 atmosphere, the in-
crease in thermal stability imparted by the fullerene nanoparticles Fig. 4. Total mass percentage and derivative thermogravimetry (inset) obtained from
TGA of PS/fullerene nanocomposites under Air atmosphere.
is relatively small. In the case of the PS-C60 nanocomposites, the
main relative gains in thermal stability are obtained with the
addition of 1.0 wt% of C60, and these are 9.3
C (DT2%), 4.7
C PCBM, in nitrogen, at 350
C. After 1 h at 350
C in nitrogen, the
(DT5%), 3.2 (DT10%), 1.3
C (DT50%) and 0.1
C (DTmax). Although total mass loss suffered by the pristine PS and by the two com-
the composite with 3.0 wt% C60 has higher thermal stability than posites with 1.0 wt% C60 and 1.0 wt% PCBM is, respectively, ca.
the composite with 1.0 wt% C60, the difference between the two is 44.0 wt%, 36.3 wt% and 20.9 wt%. These results corroborate the
marginal: D(DT2%) ¼ 0.7
C; D(DT5%) ¼ 0.6
C; D(DT10%) ¼ 0.7
C; results from Fig. 2 and Table 2 showing unequivocally that,
D(DT50%) ¼ 0.4
C and D(DTmax) ¼ 0.0
C. although both fullerenes improve the thermal stability of PS, PCBM
As also evidenced in Fig. 2 and Table 2, the composite which imparts to the polymer a greater thermal stability than C60.
shows the highest thermal stability in nitrogen is the composite
with 1.0 wt% PCBM, and its corresponding improvements in ther-
mal stability compared to the pristine polymer are: 11.6
C (DT2%), 3.2. Thermo-oxidative stability of PS/fullerene nanocomposites (air
7.0
C (DT5%), 5.2
C (DT10%), 4.5
C (DT50%) and 2.2
C (DTmax). atmosphere)
Fig. 3, shows the isothermal thermogravimetry results of pris-
tine PS and of the two PS composites with 1.0 wt% C60 and 1.0 wt% The thermal degradation curves of PS and its composites in air

Table 2
Thermal stability (nitrogen atmosphere) of PS and the corresponding fullerene nanocomposites.

Polymer Nano-particle wt% PS wt% fullerene Atmosphere T2% DT2% T5% DT5% T10% DT10% T50% DT50% Tmax DTmax
PS e 100 0 N2 363.8 e 383.0 e 394.9 e 419.9 e 424.6 e
PS C60 99.0 1.0 N2 373.1 9.3 387.7 4.7 398.1 3.2 421.2 1.3 424.7 0.1
PS C60 97.0 3.0 N2 373.8 10.0 388.3 5.3 398.8 3.9 421.6 1.7 424.7 0.1
PS PCBM 99.0 1.0 N2 375.4 11.6 390.0 7.0 400.1 5.2 424.4 4.5 426.8 2.2
 P. Pereira et al. / Polymer Testing 47 (2015) 130e136 133

atmosphere are shown in Fig. 4.

The thermo-oxidative degradation of the extruded pure PS oc-
curs in one main stage. It begins at ca. 280
C, from ca. 320
C until
ca. 425
C is displays a fast and extensive volatilization and at
430
C it has degraded completely.
The degradation of the PS-C60 composites in air occurs in two
main stages. The first volatilization stage corresponds mainly to the
degradation of the polymer, and for the composites with 1.0 wt%
C60, 3.0 wt% C60 and 1.0 wt% PCBM it starts, respectively, at ca.
305
C, 310
C and 320
C. Then, the three composites start
degrading very rapidly at ca. 335
C, 340
C and 360
C, respectively,
and when 440
C is reached they have already degraded almost
completely except for the fullerene deposit. The second volatiliza-
tion stage corresponds mainly to the thermo-oxidative degradation
of the fullerene residues. It starts at ca. 440
C for all the composites
and ends in the temperature interval from 530
C (99PS:1C60 and
99PS:1PCBM) to 575
C (97PS:3C60).
Table 3, compares the main thermo-oxidative results
Fig. 5. Isothermal thermogravimetry, for 60 min, at 275
C (solid lines) and 300
C
obtained for the different PS composites with the results of the (dash-dotted lines) of the composites PS þ 1%C60 (black) and PS þ 1%PCBM (red) in air
pure PS. As clearly shown, the thermo-oxidative stability of atmosphere. (For interpretation of the references to color in this figure legend, the
the different composites increases in the order reader is referred to the web version of this article.)
PS / 99PS:1C60 / 97PS:3C60 / 99PS:1PCBM. This is clearly
visible, for example, by comparing the corresponding temperatures
at 2 wt% mass loss (i.e. T2%) which are 317.4
C (PS), 329.0
C
(99PS:1C60), 335.7
C (97PS:3C60) and 351.9
C (99PS:1PCBM).
In air, Fig. 4 shows clearly that the composites are more stable
than the pristine polymer. Therefore, we have focused our
isothermal thermogravimetry studies on comparing the two com-
posites with 1.0 wt% C60 and 1.0 wt% PCBM. Fig. 5 shows repre-
sentative results of the two PS composites with 1.0 wt% fullerene
loading, in air atmosphere, at temperatures of 275
C and 300
C.
After 1 h at 275
C in air, the total mass loss suffered by the com-
posites with 1.0 wt% C60 and 1.0 wt% PCBM is, respectively, ca.
11.4 wt% and 5.1 wt%. The corresponding values at 300
C are
24.7 wt% and 13.9 wt%. These results show unequivocally that the
thermo-oxidative stability effect of PCBM in polystyrene is superior
to that of C60.

3.3. Thermal stability of PMMA/fullerene nanocomposites (N2

atmosphere)
The TGA and DTG (inset) results obtained in nitrogen for the
melt-processed PMMA/fullerene nanocomposites are shown in
Fig. 6.
In nitrogen, the degradation of pure PMMA displays one main
reaction step, as evidenced by the single peak curve obtained in the
corresponding DTG. Although this observation contrasts with the
results we have presented in our previous work [52], this is not
surprising as the PMMA used in the present work is different from
the PMMA we have used previously.
In the literature there is a wide variation in the thermal
degradation behavior of PMMA under inert atmosphere,
with some works reporting a single-step degradation
[12,23,30,34e36,38,40,41,51,59] while others describe a multi-step
degradation process [9,17,18,21,27,33,39,52,60,61]. It is, however,
known that these variations in thermal degradation mechanism
Fig. 6. Total mass percentage and derivative thermogravimetry (inset) obtained from
TGA of PMMA/fullerene nanocomposites under N2 atmosphere.
can be explained in terms of the structural differences between the
different PMMAs tested [62] as a consequence of the different
conditions used in their preparation (free-radical polymerization,
anionic polymerization, etc …).
As also shown in Fig. 6, all the PMMA-fullerene nanocomposites
also degrade through a single step mechanism, as evidenced by the
single peak curves obtained in the corresponding DTGs, and this
degradation step clearly moves to higher temperatures with the
addition of the fullerene nanoparticles.
PMMA starts degrading at ca. 270
C, and from ca. 290
C up to
ca. 425
C it shows an abrupt mass loss. At 425
C, complete
degradation has occurred leaving no residue. The maximum rate of

Table 3
Thermo-oxidative stability (air atmosphere) of PS and the corresponding fullerene nanocomposites.

Polymer Nano-particle wt% PS wt% fullerene Atmosphere T2% DT2% T5% DT5% T10% DT10% T50% DT50% Tmax DTmax
PS e 100 0 Air 317.4 e 332.7 e 348.2 e 395.9 e 406.0 e
PS C60 99.0 1.0 Air 329.0 11.6 347.2 14.5 363.7 15.5 404.8 8.9 414.0 8.0
PS C60 97.0 3.0 Air 335.7 18.3 353.7 21.0 369.3 21.1 407.5 11.6 414.9 8.9
PS PCBM 99.0 1.0 Air 351.9 34.5 367.1 34.4 379.0 30.8 410.8 14.9 416.6 10.6
134 P. Pereira et al. / Polymer Testing 47 (2015) 130e136

degradation, corresponding to the peak maximum in the DTG curve

occurs at 377.8
C. The PMMA-fullerene nanocomposites start
degrading at ca. 330
C, display an abrupt mass loss from ca. 350
C
up to ca. 440
C, and at 450
C they have degraded almost
completely leaving no residue other than the fullerene residue
which remains until the end of the experiments at 600
C.
The main results obtained for the different PMMA composites in
nitrogen are summarized in Table 4. As shown in Fig. 6 and Table 4,
the improvements in thermal stability at 2.0 wt% mass loss, i.e.,
DT2%, are 39.8
C, 48.1
C and 52.4
C for the composites with 1.0 wt
% C60, 3.0 wt% C60 and 1.0 wt% PCBM, respectively. Although the
composite with 3.0 wt% C60 displays initially a clearly higher
thermal stability than the composite with 1.0 wt% C60, for higher
temperatures the difference between both disappears. On the other
hand, the PCBM composite is clearly the one with the highest
thermal stability throughout the whole temperature range.
Fig. 7 shows the isothermal thermogravimetry results obtained
for pristine PMMA and for the two PMMA composites with 1.0 wt% Fig. 7. Isothermal thermogravimetry, for 60 min, at 325
C of the PMMA pure (black)
C60 and 1.0 wt% PCBM, in nitrogen, at 325
C. After 1 h at 325
C in and the composites PMMA þ 1%C60 (red) and PMMA þ 1%PCBM (blue), in nitrogen
nitrogen, the total mass loss suffered by the pristine PMMA and by atmosphere. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
the two composites with 1.0 wt% C60 and 1.0 wt% PCBM is,
respectively, ca. 57.2 wt%, 26.8 wt% and 20.8 wt%. These results
reinforce the results from Fig. 6 and Table 4 showing, once again,
that similarly to the results obtained with PS composites, in PMMA
composites the thermal stability effect imparted by the PCBM
nanoparticles is also superior to that of C60 nanoparticles.

3.4. Thermo-oxidative stability of PMMA/fullerene nanocomposites

(air atmosphere)

Fig. 8 shows the TGA and DTG (inset) results obtained in air for
the melt-processed PMMA/fullerene nanocomposites.
In air, pristine PMMA starts degrading at ca. 250
C and suffers
an abrupt volatilization in the temperature range between ca.
275
C and ca. 400
C. At 410
C, complete volatilization has
occurred leaving no residue.
The volatilization of the PMMA-C60 composites in air occurs in
two main stages. The first stage starts at ca. 300
C and ends at ca.
415
C, being very intense in the temperature range from ca. 320
C
up to ca. 415
C. This volatilization stage is mainly due to degra-
Fig. 8. Total mass percentage and derivative thermogravimetry (inset) obtained from
dation of the PMMA, and at 415
C the mass residues still present TGA of PMMA/fullerene nanocomposites under Air atmosphere.
correspond essentially to the fullerenes which have still not
degraded. The second volatilization stage starts at ca. 415
C and
ends at ca. 550
C, and corresponds to the full oxidation of the 1.0 wt% PCBM displays the highest thermo-oxidative stability
fullerene nanoparticles. throughout all the temperature range, except for temperatures
The volatilization of the PMMA-PCBM nanocomposites in air above 415
C where full degradation has nearly occurred.
also occurs in two main stages but, when compared to the PMMA- In air, Fig. 8 shows that the PMMA composites are clearly more
C60 nanocomposites, the first stage starts slightly latter at ca. 310
C stable than the pristine PMMA. Therefore, we have focused our
and displays an abrupt mass loss from ca. 330
C up to ca. 415
C. isothermal thermogravimetry studies on comparing the two com-
The second volatilization stage starts at ca. 415
C and ends at ca. posites with 1.0 wt% C60 and 1.0 wt% PCBM. Fig. 9 shows repre-
500
C, and corresponds to the full degradation of the PCBM sentative isothermal thermogravimetry results of the two PMMA
nanoparticles. composites with 1.0 wt% C60 and 1.0 wt% PCBM, in air atmosphere
Table 5 summarizes the main results obtained for the different at temperatures of 275
C and 300
C. After 1 h at 275
C in air, the
PMMA composites in air. As shown, the thermo-oxidative stability total volatilization experienced by the composites with 1.0 wt% C60
of the composite with 1.0 wt% C60 is marginally higher than that of and 1.0 wt% PCBM is, respectively, ca. 50.5 wt% and 6.4 wt%. The
the composite with 3.0 wt% C60. Furthermore, the composite with corresponding values at 300
C are 68.5 wt% and 47.2 wt%.

Table 4
Thermal stability (nitrogen atmosphere) of PMMA and the corresponding fullerene nanocomposites.

Polymer Nano-particle wt% PMMA wt% fullerene Atmosphere T2% DT2% T5% DT5% T10% DT10% T50% DT50% Tmax DTmax
PMMA e 100 0 N2 283.1 e 311.9 e 334.0 e 372.7 e 377.8 e
PMMA C60 99.0 1.0 N2 322.9 39.8 348.0 36.1 358.4 24.4 386.0 13.3 389.0 11.2
PMMA C60 97.0 3.0 N2 331.2 48.1 348.0 36.1 357.6 23.6 384.5 11.8 386.9 9.1
PMMA PCBM 99.0 1.0 N2 335.5 52.4 355.4 43.5 364.4 30.4 390.1 17.4 392.1 14.3
 P. Pereira et al. / Polymer Testing 47 (2015) 130e136 135

Table 5
Thermo-oxidative stability (air atmosphere) of PMMA and the corresponding fullerene nanocomposites.

Polymer Nano-particle wt% PMMA wt% fullerene Atmosphere T2% DT2% T5% DT5% T10% DT10% T50% DT50% Tmax DTmax
PMMA e 100 0 Air 280.1 e 296.5 e 307.3 e 340.1 e 348.0 e
PMMA C60 99.0 1.0 Air 302.4 22.3 320.9 24.4 332.1 24.8 370.7 30.6 380.5 32.5
PMMA C60 97.0 3.0 Air 303.4 23.3 318.2 21.7 328.4 21.1 367.1 27.0 374.7 26.7
PMMA PCBM 99.0 1.0 Air 323.5 43.4 338.7 42.2 348.4 41.1 380.0 39.9 383.8 35.8

matrices, moving from a region of higher concentration to a region

of lower concentration across a concentration gradient (Fick's laws
of diffusion), and favoring their better dispersion at a molecular
level. Such PCBM diffusion has been previously observed in other
polymer-PCBM systems [63e65].
For the particular case of polystyrene, previous reports have
shown that the miscibility limits of C60 and PCBM are, respectively,
ca. 1 wt% [66] and ca. 15 wt% [67], where the miscibility limit is
understood as the maximum loading of nanoparticles that can be
inside the polymer matrix before they start a process of
thermodynamically-driven segregation from the matrix. On the
other hand, there are still no reports in the literature on the ther-
modynamic compatibility between the PMMA matrix and the ful-
lerenes C60 and PCBM. However, as PMMA is a very polar polymer, it
is predictable that the polar PCBM molecule will also disperse much
better in PMMA than the nonpolar C60 molecule.

Fig. 9. Isothermal thermogravimetry, for 60 min, at 275
C (solid lines) and 300
C
(dash-dotted lines) of the composites PMMA þ 1%C60 (black) and PMMA þ 1%PCBM
(red) in air atmosphere. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
3.5. General comparison of results
A comparison of the results in Tables 2 and 4 shows that the
thermal stability effect of the fullerenes is higher in PMMA than in
PS. For example, the values of DT2% for the three composites with
1.0 wt% C60, 3.0 wt% C60 and 1.0 wt% PCBM are, respectively, 9.3
C,
10.0
C and 11.6
C in polystyrene and are 39.8
C, 48.1
C and
52.4
C in PMMA.
A comparison of the results in Tables 3 and 5 shows that the
thermo-oxidation stability effect of the fullerenes is also higher in
PMMA than in PS. Considering, for example, the values of DT2% for
the three composites with 1.0 wt% C60, 3.0 wt% C60 and 1.0 wt%
PCBM, these are 11.6
C, 18.3
C and 34.5
C, respectively, for the PS
composites and 22.3
C, 23.3
C and 43.4
C, respectively, for the
corresponding PMMA composites.
More importantly, and as discussed in the previous sections, the
improvements in thermal stability (N2 atmosphere) and in thermo-
oxidation stability (air atmosphere) observed for the PS and PMMA
composites with PCBM are systematically higher than the im-
provements observed in the corresponding composites with C60.
These results are in good general agreement with the results from
our previous studies, using solution blended composites of poly-
styrene [46] and PMMA [52], with much higher fullerene loadings.
Although PCBM has lower thermal and thermo-oxidative sta-
bility than C60 [46,52], the polymer-PCBM composites have higher
thermal and thermo-oxidative stability than the corresponding
polymer-C60 composites. This apparent contradiction can be
explained by the fact that PCBM disperses more homogeneously in
the polymer matrices than the C60 for the following reasons: (i)
PCBM has an organic ligand which helps compatibilization with the
polymer; (ii) contrary to C60, PCBM has a relatively low melting
temperature (Tm (PCBM) ~280
C) and, therefore, during the ther-
mogravimetry tests at temperatures above Tm (PCBM), the PCBM
molecules are in a liquid state and free to diffuse inside the polymer
4. Conclusions
In this work, we have studied and compared the thermal and
thermo-oxidation stability effect imparted by the two different
fullerenes C60 and PCBM on polystyrene and PMMA composites.
Our results show that PCBM is more effective than C60 at improving
the thermal and thermo-oxidative stability of the corresponding PS
and PMMA composites. Furthermore, the fullerenes are more
effective at improving the thermal and thermo-oxidative stability
of PMMA than that of polystyrene.
Acknowledgments
This work was funded by FEDER funds through the COMPETE
2020 Program and National Funds through FCT e Portuguese
Foundation for Science and Technology under the project UID/CTM/
50025/2013. Funding from FEDER through the program COMPETE
(Project EXPL/CTM-POL/0933/2012) is also acknowledged.
References
[1] B.N. Jang, C.A. Wilkie, The thermal degradation of polystyrene nanocomposite,
Polymer 46 (9) (2005) 2933e2942.
[2] S. Bourbigot, J.W. Gilman, C.A. Wilkie, Kinetic analysis of the thermal degra-
dation of polystyrene-montmorillonite nanocomposite, Polym. Degrad. Stab.
84 (3) (2004) 483e492.
[3] S.V. Krishna, G. Pugazhenthi, Properties and thermal degradation kinetics of
polystyrene/organoclay nanocomposites synthesized by solvent blending
method: effect of processing conditions and organoclay loading, J. Appl.
Polym. Sci. 120 (3) (2011) 1322e1336.
[4] H.-W. Wang, et al., Synthesis and dielectric properties of polystyrene-clay
nanocomposite materials, J. Appl. Polym. Sci. 91 (2) (2004) 1368e1373.
[5] C.-R. Tseng, et al., Preparation and characterization of polystyreneeclay
nanocomposites by free-radical polymerization, J. Appl. Polym. Sci. 85 (7)
(2002) 1370e1377.
[6] M. Ho Kim, et al., Synthesis and material properties of syndiotactic poly-
styrene/organophilic clay nanocomposites, J. Appl. Polym. Sci. 92 (4) (2004)
2144e2150.
[7] R. Qi, et al., Synthesis and properties of polystyreneeclay nanocomposites via
in situ intercalative polymerization, J. Appl. Polym. Sci. 97 (1) (2005) 201e207.
[8] A.K. Dhibar, et al., Effect of clay platelet dispersion as affected by the
manufacturing techniques on thermal and mechanical properties of PMMA-
clay nanocomposites, J. Appl. Polym. Sci. 113 (5) (2009) 3012e3018.
[9] Z. Gao, et al., The characterization of organic modified montmorillonite and its
136 P. Pereira et al. / Polymer Testing 47 (2015) 130e136
filled PMMA nanocomposite, J. Therm. Anal. Calorim. 64 (2) (2001) 467e475.
[10] A. Laachachi, et al., Use of oxide nanoparticles and organoclays to improve
thermal stability and fire retardancy of poly(methyl methacrylate), Polym.
Degrad. Stab. 89 (2) (2005) 344e352.
[11] P. Lu, The effects of different grafted clays on thermal properties of their
PMMA composites, Polym. Plast. Technol. Eng. 50 (15) (2011) 1541e1545.
[12] P. Pandey, et al., Flammability and thermal characterization of PMMA/clay
nanocomposites and thermal kinetics analysis, Polym. Compos. 33 (11) (2012)
2058e2071.
[13] W.S. Wang, et al., Transparent and flame retardant PMMA/clay nano-
composites prepared with dual modified organoclay, Polym. Adv. Technol. 23
(3) (2012) 625e631.
[14] Y. Xu, et al., Effect of clay type on morphology and thermal stability of
PMMAeclay nanocomposites prepared by heterocoagulation method, Poly-
mer 45 (11) (2004) 3735e3746.
[15] L. Qiu, B. Qu, Preparation and characterization of surfactant-free polystyrene/
layered double hydroxide exfoliated nanocomposite via soap-free emulsion
polymerization, J. Colloid Interface Sci. 301 (2) (2006) 347e351.
[16] L. Qiu, W. Chen, B. Qu, Structural characterisation and thermal properties of
exfoliated polystyrene/ZnAl layered double hydroxide nanocomposites pre-
pared via solution intercalation, Polym. Degrad. Stab. 87 (3) (2005) 433e440.
[17] G.-A. Wang, C.-C. Wang, C.-Y. Chen, The disorderly exfoliated LDHs/PMMA
nanocomposites synthesized by in situ bulk polymerization: the effects of
LDH-U on thermal and mechanical properties, Polym. Degrad. Stab. 91 (10)
(2006) 2443e2450.
[18] C. Manzi-Nshuti, et al., The role of the trivalent metal in an LDH: synthesis,
characterization and fire properties of thermally stable PMMA/LDH systems,
Polym. Degrad. Stab. 94 (4) (2009) 705e711.
[19] J. Kuljanin-Jakovljevic, et al., Thermal degradation kinetics of polystyrene/
cadmium sulfide composites, Polym. Degrad. Stab. 94 (6) (2009) 891e897.
[20] Y.-W. Yan, et al., Flame retardance and thermal degradation mechanism of
polystyrene modified with aluminum hypophosphite, Polym. Degrad. Stab. 99
(2014) 35e42.
[21] Y.-H. Hu, C.-Y. Chen, C.-C. Wang, Viscoelastic properties and thermal degra-
dation kinetics of silica/PMMA nanocomposites, Polym. Degrad. Stab. 84 (3)
(2004) 545e553.
[22] R. Pantaleo n, J. Gonzalez-Benito, Structure and thermostability of PMMA in
PMMA/silica nanocomposites: effect of high-energy ball milling and the
amount of the nanofiller, Polym. Compos. 31 (9) (2010) 1585e1592.
[23] M.L. Saladino, et al., The effect of silica nanoparticles on the morphology,
mechanical properties and thermal degradation kinetics of PMMA, Polym.
Degrad. Stab. 97 (3) (2012) 452e459.
[24] M. Salami-Kalajahi, et al., A study on the properties of PMMA/silica nano-
composites prepared via RAFT polymerization, J. Polym. Res. 19 (2) (2012)
1e11.
[25] D.Q. Zou, H. Yoshida, Size effect of silica nanoparticles on thermal decompo-
sition of PMMA, J. Therm. Anal. Calorim. 99 (1) (2010) 21e26.
[26] H.W.P. Carvalho, et al., Structure and thermal behavior of
PMMAepolysilsesquioxane organiceinorganic hybrids, Polym. Degrad. Stab.
104 (0) (2014) 112e119.
[27] M. Pal, B. Singh, J. Gautam, Thermal stability and UV-shielding properties of
polymethyl methacrylate and polystyrene modified with calcium carbonate
nanoparticles, J. Therm. Anal. Calorim. 107 (1) (2012) 85e96.
[28] N. Cinausero, et al., Impact of modified alumina oxides on the fire properties
of PMMA and PS nanocomposites, Polym. Adv. Technol. 22 (12) (2011)
1931e1939.
[29] W. Viratyaporn, R. Lehman, Effect of nanoparticles on the thermal stability of
PMMA nanocomposites prepared by in situ bulk polymerization, J. Therm.
Anal. Calorim. 103 (1) (2011) 267e273.
[30] A. Laachachi, et al., Influence of Sb2O3 particles as filler on the thermal sta-
bility and flammability properties of poly(methyl methacrylate) (PMMA),
Polym. Degrad. Stab. 85 (1) (2004) 641e646.
[31] A. Laachachi, et al., Influence of TiO2 and Fe2O3 fillers on the thermal prop-
erties of poly(methyl methacrylate) (PMMA), Mater. Lett. 59 (1) (2005)
36e39.
[32] E. Dzunuzovi c, et al., Thermal properties of PMMA/TiO2 nanocomposites
prepared by in-situ bulk polymerization, Polym. Compos. 30 (6) (2009)
737e742.
[33] M.M. Demir, et al., PMMA/zinc oxide nanocomposites prepared by in-situ bulk
polymerization, Macromol. Rapid Commun. 27 (10) (2006) 763e770.
[34] F. Laoutid, et al., Effect of magnesium dihydroxide nanoparticles on thermal
degradation and flame resistance of PMMA nanocomposites, Polym. Adv.
Technol. 22 (12) (2011) 1713e1719.
[35] V.V. Vodnik, et al., Thermal and optical properties of silver-
epoly(methylmethacrylate) nanocomposites prepared by in-situ radical
polymerization, Eur. Polym. J. 46 (2) (2010) 137e144.
[36] T.E. Motaung, et al., PMMAetitania nanocomposites: Properties and thermal
degradation behaviour, Polym. Degrad. Stab. 97 (8) (2012) 1325e1333.
[37] T.E. Motaung, et al., Morphology, mechanical properties and thermal
degradation kinetics of PMMA-zirconia nanocomposites prepared by melt
compounding, Express Polym. Lett. 6 (11) (2012) 871e881.
[38] T.C. Chang, et al., Effect of phenolic phosphite antioxidant on the thermo-
oxidative degradation of PMMA, Polym. Degrad. Stab. 77 (1) (2002) 29e34.
[39] P. Gałka, J. Kowalonek, H. Kaczmarek, Thermogravimetric analysis of thermal
stability of poly(methyl methacrylate) films modified with photoinitiators,
J. Therm. Anal. Calorim. 115 (2) (2014) 1387e1394.
[40] C.-H. Chen, et al., Preparation, characterization, and thermal stability of novel
PMMA/expandable graphite halogen-free flame retardant composites, Polym.
Compos. 31 (1) (2010) 18e24.
[41] C.-F. Kuan, et al., Synthesis, characterization, flame retardance and thermal
properties of halogen-free expandable graphite/PMMA composites prepared
from solegel method, Polym. Degrad. Stab. 93 (7) (2008) 1357e1363.
[42] A.O. Pozdnyakov, et al., Thermal decomposition study of poly(methyl meth-
acrylate)/carbon nanofiller composites, Polym. Adv. Technol. 22 (1) (2011)
84e89.
[43] B.B. Troitskii, et al., Inhibition of thermo-oxidative degradation of poly(methyl
methacrylate) and polystyrene by C60, Eur. Polym. J. 36 (5) (2000)
1073e1084.
[44] E.B. Zeinalov, G. Koßmehl, Fullerene C60 as an antioxidant for polymers,
Polym. Degrad. Stab. 71 (2) (2001) 197e202.
[45] J.-W. Kim, et al., Preparation and characterizations of C60/polystyrene com-
posite particle containing pristine C60 clusters, Bull. Korean Chem. Soc. 33 (9)
(2012) 2966e2970.
[46] L. Fernandes, H. Gaspar, G. Bernardo, Inhibition of thermal degradation of
polystyrene by C60 and PCBM: A comparative study, Polym. Test. 40 (0)
(2014) 63e69.
[47] B.B. Troitskii, et al., Retardation of thermal degradation of PMMA and PVC by
C60, Eur. Polym. J. 33 (10e12) (1997) 1587e1590.
[48] B.M. Ginzburg, et al., The effect of fullerene C60 on the thermooxidative
degradation of a free-radical PMMA studied by thermogravimetry and calo-
rimetry, Tech. Phys. Lett. 27 (10) (2001) 806e809.
[49] K.B. Zhogova, et al., Investigation of fullerene C60 effect on properties of
polymethylmethacrylate exposed to ionizing radiation, Eur. Polym. J. 41 (6)
(2005) 1260e1264.
[50] V.V. Zuev, F. Bertini, G. Audisio, Fullerene C60 as stabiliser for acrylic poly-
mers, Polym. Degrad. Stab. 90 (1) (2005) 28e33.
[51] L. Zhao, et al., The effect of fullerene on the resistance to thermal degradation
of polymers with different degradation processes, J. Therm. Anal. Calorim. 115
(2) (2014) 1235e1244.
[52] H. Gaspar, et al., Enhanced thermal stability of poly(methyl methacrylate)
composites with fullerenes, Polym. Bull. (2015) 1e12.
[53] S. Jipa, et al., Chemiluminescence investigation of thermo-oxidative degra-
dation of polyethylenes stabilized with fullerenes, Polym. Degrad. Stab. 80 (2)
(2003) 209e216.
[54] P. Pereira, et al., Melt processed polyethylene/fullerene nanocomposites with
highly improved thermo-oxidative stability, Polym. Test. 45 (0) (2015)
124e131.
[55] H. Liu, et al., Thermal degradation and flammability properties of HDPE/EVA/
C60 nanocomposites, Thermochim. Acta 506 (1e2) (2010) 98e101.
[56] G. Bernardo, D.G. Bucknall, Recent progress in the understanding and
manipulation of morphology in polymer: fullerene photovoltaic cells, Opto-
electron. Adv. Mater. Devices (2013) Chapter 9, 207e227.
[57] A. Rodrigues, et al., Thermal stability of P3HT and P3HT: PCBM blends in the
molten state, Polym. Test. 32 (7) (2013) 1192e1201.
[58] H. Gaspar, et al., Increase in thermo-oxidation stability of conjugated poly-
mers at high temperatures, Polym. Test. 34 (0) (2014) 183e191.
[59] M. Arshad, et al., The effect of AlBr3 additive on the thermal degradation of
PMMA a study using TG-DTA-DTG, IR and PY-GC-MS techniques, J. Therm.
Analy. Calorim. 96 (3) (2009) 873e881.
[60] J.D. Peterson, S. Vyazovkin, C.A. Wight, Kinetic study of stabilizing effect of
oxygen on thermal degradation of poly(methyl methacrylate), J. Phys. Chem. B
103 (38) (1999) 8087e8092.
[61] M. Ferriol, et al., Thermal degradation of poly(methyl methacrylate) (PMMA):
modelling of DTG and TG curves, Polym. Degrad. Stab. 79 (2) (2003) 271e281.
[62] B.J. Holland, J.N. Hay, The effect of polymerisation conditions on the kinetics
and mechanisms of thermal degradation of PMMA, Polym. Degrad. Stab. 77
(3) (2002) 435e439.
[63] N.D. Treat, et al., Interdiffusion of PCBM and P3HT reveals miscibility in a
photovoltaically active blend, Adv. Energy Mater. 1 (1) (2011) 82e89.
[64] N.D. Treat, et al., Temperature dependence of the diffusion coefficient of PCBM
in poly(3-hexylthiophene), Macromolecules 46 (3) (2013) 1002e1007.
[65] B. Watts, et al., A quantitative study of PCBM diffusion during annealing of
P3HT: PCBM blend films, Macromolecules 42 (21) (2009) 8392e8397.
[66] K. Campbell, et al., Role of conformation in pi-pi interactions and polymer/
fullerene miscibility, J. Phys. Chem. B 115 (29) (2011) 8989e8995.
[67] D.G. Bucknall, et al., Phase-morphology and molecular structure correlations
in model fullerene-polymer nanocomposites, in: A. Boudenne (Ed.), Polymer
Composite Materials: from Macro, Micro to Nanoscale, 2012, pp. 63e66.