Journal of Cleaner Production xxx (2015) 1e8

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Journal of Cleaner Production

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

Sustainable eco-composites obtained from agricultural and urban

waste plastic blends and residual cellulose fibers
J. Martínez Urreaga a, e, *, C. Gonza
lez-Sa

nchez b, A. Martínez-Aguirre b,
C. Fonseca-Valero c, e, J. Acosta c, M.U. de la Orden d, e
a
Departamento de Ingeniería Química Industrial y del Medio Ambiente, E.T.S.I. Industriales, Universidad Polit
ecnica de Madrid, Jos
e Guti

errez Abascal, 2.
28006 Madrid, Spain
b
Departamento de Ingeniería Química y Tecnología del Medio Ambiente, Universidad de Oviedo, Avda. Julia
n Clavería, 8. 33006 Oviedo, Spain
c
Departamento de Ingeniería Meca
nica, Química y Disen
~ o Industrial, E.T.S.I. Disen
~ o Industrial, Universidad Polit

ecnica de Madrid, Ronda de Valencia, 3.
28012 Madrid, Spain
d
Departamento de Química Orga


nica I, Universidad Complutense de Madrid, Facultad de Optica
n, s/n. 28037 Madrid, Spain
y Optometría, C/ Arcos de Jalo
e
Polymers, Characterization and Applications Research Group, Spain

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

Article history: The use of blends of recycled agricultural plastic and post-consumer high-density polyethylene from
Received 28 March 2015 municipal solid wastes, as matrices for sustainable eco-composites, was investigated with the aim of
Received in revised form boosting the use of recycled materials and reducing the waste plastic environmental impact. It was
2 June 2015
proposed that proper selection of blends of different waste plastics will allow the production of com-
Accepted 2 June 2015
Available online xxx
posites with optimized properties. The two plastics and their blends were characterized by using
different spectroscopic techniques and thermal analysis, and measuring the flow curves. The eco-
composites were obtained by compounding a selected blend of recycled agricultural plastic and post-
Keywords:
Recycling
consumer polyethylene with different proportions of coupling agent and waste cellulose fibers in a
Agricultural waste plastics pilot-plant twin-screw extruder. The structure of the final materials and the role of the coupling agent
Eco-composites were analyzed by using scanning electron microscopy. Finally, the novel eco-composites were compared
Biocomposites to their counterparts without post-consumer polyethylene, revealing that the incorporation of poly-
Mechanical properties ethylene increases the strength and stiffness of the eco-composites, without compromising the impact
strength. The incorporation of 40 wt% of polyethylene caused increases in moduli as high as 175% for the
polymer and 47% for composites with 30% of fibers. The tensile strength increased up to 21% for the same
composites. The decreases in processability caused by the incorporation of polyethylene can be corrected
by increasing the coupling agent content. The improved balance between stiffness, strength and
toughness without compromising processability can increase the recyclability of the polymer and cel-
lulose wastes used in this work.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction wastes are mechanically recycled. For example, in Europe,

In the last decades the fraction of plastic waste subjected to
mechanical recycling has increased substantially, mainly due to the
growing interest of society for environmental and sustainability
issues (PlasticsEurope, 2014; Al-Salem et al., 2010; Hopewell et al.,
2009). However, even today only minor amounts of the plastic
* Corresponding author. Departamento de Ingeniería Química Industrial y del
Medio Ambiente, E.T.S.I. Industriales, Universidad Polite
cnica de Madrid, Jose

than the virgin plastic (although this comparison may change

rrez Abascal, 2. 28006 Madrid, Spain. Tel.: þ34 913363183.
Gutie
E-mail address: joaquin.martinez@upm.es (J. Martínez Urreaga).
including the EU-27 countries, Norway and Switzerland, the
collected post-consumer waste reached 25.2 Mt in 2012 but, out of
these, only 6.6 Mt (26.3%) were mechanically recycled and 8.9 Mt
(35.6%) were sent to energy recovery, while 9.6 Mt (38.1%) were still
sent to landfill, leaving much room for improving recycling rates
(PlasticsEurope, 2014).
To explain this fact the costs of collection, cleaning, sorting and
processing of waste must be taken into account. For many highly
contaminated residues the recycled plastic can have a price higher
depending on the evolution of oil prices) (Briassoulis et al., 2013).

http://dx.doi.org/10.1016/j.jclepro.2015.06.001
0959-6526/© 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
2 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8
Moreover, the plastic wastes contain polymers with different de-
grees of degradation and contamination, so the recycled plastics
have widely varying performances, compromising the demand for
these materials in the market. This issue is very important, since Al-
Salem et al. (2014) have shown that the potential of the market for
absorbing recycled materials is one of the key factors that must be
considered for selecting the appropriate waste treatment
processes.
Therefore, the development of costeeffective processes for
improving the performance of the recycled plastics is required in
order to increase the recyclability of the waste plastics and phase-
out their landfilling, thus reducing their environmental impact and
helping to meet the EU targets for 2025 and 2030 regarding solid
waste treatment (European Commission, 2014). Nowadays,
different alternatives are used to achieve these improvements,
including the blending with virgin plastics, using additives for the
re-gradation or incorporating reinforcements to make composites
with enhanced mechanical properties. When the reinforcement
comes from natural sources, as cellulose-based fibers, composites
are usually known as biocomposites or eco-composites (Gonza
lez-

nchez et al., 2014; Kitagawa et al., 2005; Yam and Mak, 2014).
Sa
The results obtained in a recent work have shown that it is
possible to obtain composite materials with good properties by
compounding recycled agricultural plastic (RAP), whose major
component is low-density polyethylene (LDPE), with waste cellu-
lose fibers (WCF) and a coupling agent (Gonza
lez-Sa
nchez et al.,
2014). The cellulose fibers allow increasing the stiffness and
strength of the recycled plastic, at a very low cost, and the coupling
agent is required to overcome the problems derived from the poor
interfacial adhesion of the cellulose with hydrophobic polymers
such as polyethylene (PE) and polypropylene (PP) (de la Orden
et al., 2007; Faruk et al., 2012; Kazemi Najafi, 2013; Koronis et al.,
2013; La Mantia and Morreale, 2006). The manufacturing of these
eco-composites from waste cellulose and recycled agricultural
plastic is a suitable way for increasing waste recovery and
improving the sustainability of the products manufactured thereof
(Al-Oqla and Sapuan, 2014; Alves et al., 2010; Bocken et al., 2014;
Gonz
alez-S

anchez et al., 2014; Le Duigou and Baley, 2014; La Rosa
et al., 2014; Mohanty et al., 2005; Wan Alwi et al., 2014).
The objectives of this work were to extend the range of the
waste plastics used in the manufacture of the eco-composites, by
including post-consumer plastics from urban waste, and improve
the properties, in a cost-effective way, in order to increase the de-
mand for these materials in the market and, hence, the recyclability
of the three waste materials (RAP, rHDPE and WCF).
Selected blends of the recycled agricultural plastic with a post-
consumer plastic (rHDPE) coming from bottles and other con-
tainers found in the urban solid waste, whose main component is
high-density polyethylene, were used as matrices for eco-
composites with waste cellulose. The use of blends of different
recycled or waste plastics as matrices for composites has been
scarcely studied to the present. However, the use of blends of virgin
polymers in different applications is well known. If the polymers
are properly selected, the different properties of each polymer can
be combined to create new blends with properties that can be even
better than those of the neat polymers (Martins et al., 2009). This
approach could also be applied to the use of mixtures of waste
plastics as matrices for composites. In this case, it can be expected
that adding rHDPE will increase the stiffness and other properties
of the final eco-composites.
RAP, rHDPE and their blends were characterized using different
spectroscopic, rheological and thermal analysis techniques. Taking
into account the results of this characterization, one of the blends
was selected to be used as matrix in the manufacture of the com-
posites. Then, the RAP/rHDPE blend was compounded with variable
Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
amounts of WCF and coupling agent in a pilot-plant twin-screw
extruder and, finally, the properties of the obtained RAP/rHDPE/
WCF eco-composites were analyzed and compared to the proper-
ties of the analogous composites obtained without rHDPE. The
comparison of the properties of the different composites revealed
that the incorporation of rHDPE is a valid alternative for improving
the strength, the stiffness and other properties of the final recycled
materials.
2. Materials and methods
The raw materials used in this work, the processing of the
composites and the methods used for characterizing the raw ma-
terials and testing the final eco-composites are described in this
section.
2.1. Materials
The recycled agricultural plastic (RAP) was supplied by BEFESA


PLASTICOS (Spain), in pellet form, as ALFATEN 200™, and comes
from greenhouse and other agricultural films used in the south and
east of Spain. The rHDPE, coming from the urban solid waste and
supplied as flakes by TERSA (Spain), was previously pelletized in
order to obtain a homogenous material and to facilitate its dosing
during melt compounding. The waste cellulose fibers (WCF), sup-
plied by ENCE-Navia (Spain), were a by-product obtained in the
manufacturing of Kraft cellulose pulp, mainly consisting of un-
bleached Eucaliptus Globulus cellulose fibers. They were ribbon-
shaped with an average length of 583.5 (53.3) mm and an average
transversal section of 12.3 (3.0) x 3.5 (0.7) mm. The coupling agent
(MAPE) was Licocene PE MA 4351 GR, a maleic anhydride-modified
polyethylene with acid number ¼ 43, supplied by Clariant Ibe
rica
(Spain). Two different concentrations of MAPE (1.5 and 3 wt %, with
regard to the total weight of composite material) were evaluated.
Materials without MAPE were also obtained as reference materials.
A 0.3 wt % of Irganox B900 (Ciba, Spain) was used as antioxidant.
2.2. Processing
The composites with 25, 30 or 35 wt % of WCF, with regard to the
total weight of composite material, were compounded in a co-
rotating intermeshing twin screw extruder, mod. ZE25 (Berstorff,
Germany). The temperature profile, from hopper to die was
155e152e149e146e143e140e137e155/170  C in all cases. The

temperature of the last zone varied between 155 and 170 C
depending on the content of cellulose and MAPE. The WCF were
previously dried at 105  C for 3 h in an air-circulating oven and the
moisture content was lower than 1 wt %. The eco-composite pellets
were dried in the same way before the injection. The test specimens
were obtained, according to the ISO 3167 standard, in an injection
molding machine, mod. METEOR 120/45 (Mateu & Sole
, Spain). The
temperature profiles, which depended on the percentage of fibers,
were 150e155e160e165  C for the unreinforced matrix,
175e180e185e188  C for the composites with 25 wt % of WCF,
180e185e188e192  C for those having 30 wt % of WCF and
185e188e191e193  C when a 35 wt % of WCF was added. The mold
temperature was set at 50  C.
2.3. Material characterization and testing
The waste plastics and their blends were characterized by
spectroscopy and thermal analysis. Ultra-Violet (UV) spectra were
taken with a UV-VIS Spectrophotometer, mod. UV-2401PC (Shi-
madzu, Japan) at 200 nm/min. Fourier Transform Infrared (FTIR)
spectra were obtained using an FTIR Spectrometer, mod. Galaxy-
 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8
3020 (Mattson, USA). Each spectrum was the result of 90 scans at a
resolution of 4 cm1. The UV and FTIR spectra were taken in
transmission mode using films molded in a hot-plates press (IQAP
LAP, Spain) at 140  C and 2 MPa. Differential Scanning Calorimetry
(DSC) was conducted by means of a calorimeter, mod. DSC 822e
(Mettler-Toledo, Switzerland) under nitrogen atmosphere. The
second heating scan, at 10  C/min, was considered for the assess-
ment of DSC traces. Shear viscosity curves were determined with a
sweep of shear rates ranging from 20 s1 to 2000 s1 at 190  C,
using a double bore capillary rheometer, mod. Rosand RhV7
(Rosand Precision Ltd., UK), having a “zero” length die for ac-
counting of die entry pressure drop, with a barrel bore inner
diameter of 23 mm, and a capillary die with an inner diameter of
2 mm and a length of 10 mm. The rheological tests were carried out
with a pre-test to assure the proper compression and molten state
of the material. Prior to rheological testing, the material was
compressed at a speed of 100 mm/min up to a pressure of 1.0 MPa,
heated for of 2 min, and compressed again to 0.5 MPa pressure.
The tensile properties were determined by using a universal
testing machine, mod. 1011 (Instron, USA), following the ISO R527
standard. The reported property values are the average of 6 speci-
mens. The fracture surfaces generated in the tensile tests were
examined by Scanning Electron Microscopy (SEM) by using a field
emission scanning electron microscope, mod. JEOL-6610LV (JEOL,
Japan).
The Charpy unnotched impact strength was determined by
means of an Izod/Charpy impact tester (JBA Instruments, Spain),
following the ISO 179 standard, being the results the average of 10
specimens. Melt flow indices were measured at 190  C using a melt
flow indexer, mod. 6942 (CEAST, Italy). Due to the high viscosity, a
3 mm-diameter nozzle and a 15 kg weight had to be used for as-
suring the flowing of the composite melt through the nozzle while
meeting the test duration times set by the ISO 1133 standard.
3. Results and discussion
This section covers the results and discussion regarding the
spectroscopic, rheological and thermal characterization of the
blend of waste plastics, the properties of the eco-composites and
the effect of the incorporation of rHDPE.
3.1. Characterization of the waste plastics and their blends
The plastics used in this work, i.e. RAP, rHDPE and their blends,
were characterized using different techniques, with the aim of
selecting a specific mixture of RAP and rHDPE to be used as matrix
for the eco-composites.
Fig. 1 shows the most interesting region of the FTIR spectra of
RAP and two RAP- rHDPE blends. In addition to the main poly-
ethylene absorptions at 1460e1470 cm1 (CH2 bending) and
720730 cm1 (CH2 rocking), the spectra of the blends show other
characteristic bands that reveal the presence of both RAP and
rHDPE. The strongest of these absorptions appear at 1740 cm1 (C]
O stretching) and 1240 cm1 (CeO stretching) and reveal the
presence of acetate groups, which proceed of the ethylene-vinyl
acetate (EVA) copolymer used in some agricultural plastics, for
example, those used in greenhouse covers. Previous results have
shown that the amount of EVA in the agricultural recycled plastics,
like that used in this work, was between 2.5 and 4.5 wt %
(Gonza
lez-Sa
nchez et al., 2014). The presence of significant
amounts of the acetate groups in the waste plastic is very inter-
esting regarding its use as matrix for cellulose-reinforced com-
posites, as it will be discussed in Section 3.2.
The spectra of the blends also show weak absorptions between
1000 and 1200 cm1, which have been assigned to the presence of
Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
3
inorganic additives and/or impurities in RAP. The appearance of a
weak absorption centered at 1535 cm1 in the spectrum of RAP,
also visible in the spectra of the blends, has been assigned to the
presence of hindered amine light stabilizers (HALS), such as Chi-
massorb 944 (Gonz
alez-S

anchez et al., 2014; Scoponi et al., 2000).
HALS and other photo-stabilizer additives are widely used in
greenhouse covers and the above results confirm that significant
amounts of valuable additives remain in the agricultural plastic
after its use, giving additional value to the recycled agricultural
plastics.
The infrared spectra also show the contributions of the rHDPE
used in the blends. In addition to the above mentioned absorption
bands, the spectra of the blends show many weak absorptions that
can be related to the presence of additives and impurities corre-
sponding to the rHDPE. For instance, the presence of PP as an im-
purity in rHDPE is revealed by the very weak bands that appear at
841, 973 and 998 cm1.
The presence of additives in the blends can be also detected
using UV spectroscopy. Fig. 2 shows the UV spectra of RAP and two
representative RAP/rHDPE blends. The spectra of the blends show a
broad band centered around 440 nm that can be more clearly
appreciated in the spectrum of the blend that contains 80 wt % of
rHDPE. As this absorption band does not appear in the spectrum of
RAP, it can be assigned to the presence of colored pigments in
rHDPE, which come from the residues of containers of multiple
colors. The spectra of the blends also show a band centered at
225 nm whose intensity is proportional to the RAP content and that
can be assigned to n-p* electronic transitions of 1,3,5-triazine
moieties in light stabilizers such as Chimassorb 944 (Scoponi et al.,
2000). Thus, the UV spectra confirm the presence in the blends of
this kind of valuable additives.
Another key issue in the selection of a specific mixture of
thermoplastics as a matrix for composite materials is the flow
behavior. The knowledge of the flow behavior in the molten state is
essential for an adequate production and processing of the com-
posites, since a main part of these takes place in that molten state.
Moreover, it must be taken into account that cellulose contents as
high as 30e60 wt % are usual in the composites reinforced with
lignocellulosic materials, which requires a particularly strict control
of the flow behavior (Li and Wolcott, 2005). Fig. 3 depicts the flow
Fig. 1. FTIR spectra of RAP and two RAP/rHDPE blends. RAP20 and RAP60 contain 20
and 60 wt % of RAP, respectively.
4 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8

curves of RAP and the blends with 40 and 80 wt % of rHDPE and

reveals that the processability of the blends depends on their
composition. From Fig. 3, it can be seen that the shear rate de-
pendency does not change with the introduction of rHDPE, but the
shear viscosity increases with increasing rHDPE content over the
whole shear rate range, especially at low shear rates. This is the
expected result, since it is well established that the rHDPE that
come from milk bottles and other containers have high melt vis-

nchez-Soto et al., 2008).
cosities (Sa
Considering that these mixtures are used in composites with
high content of cellulose fibers, the viscosity increase caused by the
introduction of rHDPE was considered as a major constraint.
Therefore, it was decided to limit the rHDPE content to 40 wt %, in
order to preserve as much as possible the processability of the final
eco-composites. This result agrees with those of Gattiglia et al.
(1993), who found that the mixtures of urban solid wastes con-
taining different PEs, PP and polystyrene maintain good mechanical
properties if the concentration of LDPE (which in our case is the
major component of RAP) is at least 60% by weight.
Finally, the selected mixture, RAP/rHDPE 60/40 by weight, was
characterized by using DSC, which allows the determination of the Fig. 3. Shear viscosity of RAP and two RAP/rHDPE blends that contain 20 and 60 wt %
polymers present in the mixture and provides useful information of RAP.

about the structure of the material. Fig. 4 shows the DSC heating
traces corresponding to RAP, rHDPE and the selected mixture. In the
Although LDPE is a major component of the blend, its melting
DSC endotherm of the mixture two main peaks are observed at 108
peak shows lower intensity in the DSC curve. This is due to the fact
and 129  C, which may be assigned to the melting of LDPE and
that LDPE is a less crystalline phase and crystallizes at lower tem-
HDPE crystallites (Fu et al., 2003).
peratures than HDPE. The solidification of LDPE takes place around
The presence of the two main peaks confirms that LDPE and
the crystallites of HDPE and, therefore, LDPE reaches lower crys-
HDPE are the main components of the mixture and indicates that
tallinity in the copolymer than in the pure homopolymer (Minick
the two polymers do not co-crystallize together in this case. This is
et al., 1995). Fig. 4 also shows that the melting peaks of LDPE and
the usual behavior, as it is well known that LDPE and HDPE form
HDPE appear in the blend at lower temperatures than in the
homogeneous materials in the melt but only co-crystallize under
separate plastics, which may be explained as a consequence of the
certain conditions, depending on the composition of the mixture
decrease of the perfection of the crystallites of the two polymers,
and the cooling rate (Wignall et al., 1995). At high cooling rates, the
due to the presence of the second polymer (Minick et al., 1995).
co-crystallization has been demonstrated (Fonseca and Harrison,
The endotherm of the blend shows another peak of very low
1998); however, when the melt is solidified at low or moderate
intensity, at around 161  C, which can be more clearly observed in
cooling rates, as in our case, a blend of the two polymers, with two
the DSC trace of rHDPE. This peak may be assigned to the melting of
defined melting peaks, is obtained.
the small amounts of PP that were previously detected in the IR
analysis of the blends.
In summary, the data obtained in the characterization of the
recycled plastics used as matrices in this work indicate that the
blends obtained from RAP and rHDPE contain LDPE and HDPE as
major components, with minor but significant amounts of EVA, PP,
photo-stabilizer (and other additives) and impurities. The presence
of rHDPE causes an increase in the melt viscosity of the blends
which was considered important, so it was decided to limit the
proportion of rHDPE in the blend and to choose the 60/40 blend,
with 40 wt % of rHDPE, as matrix for the eco-composites.

3.2. Properties of the eco-composites

After selecting the 60/40 blend for its use as matrix, the eco-
composites were prepared by compounding the plastics with
three different percentages of WCF (25, 30 and 35 wt %) and MAPE
coupling agent (0, 1.5 and 3 wt %). The average values (with their
corresponding standard deviations in brackets) of the properties of
the WCF/RAP/rHDPE eco-composites are given in Table 1.
The use of WCF as reinforcement causes great increases in the
tensile elastic modulus (Et) of the material. Composites with 35 wt
% of WCF give an elastic modulus over 4 times higher than that of
the neat blend used as matrix. There are also clear increases in the
values of the maximum tensile strength (st), in good agreement
Fig. 2. UV spectra of RAP and two RAP/rHDPE blends that contain 20 and 60 wt % of with the general behavior observed when polyolefins are rein-
RAP. forced with cellulose fibers and good fiber dispersion and

Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8 5

fibers, especially when a 3 wt% of MAPE is used (Fig. 5c). This

Fig. 4. DSC heating curves of RAP, rHDPE and the blend with 60 wt % of RAP.
interfacial adhesion are achieved (Gonza
lez-Sa

nchez et al., 2014,
2008; Borja et al., 2006). Moreover, the values of Et and st
become higher as the reinforcement content increases, which
suggests that good fiber dispersion and wetting were achieved
during melt compounding.
The values given in Table 1 show that the addition of MAPE as
coupling agent has little effect on the mechanical properties of the
eco-composites. The low effect of MAPE on the moduli can be due,
at least in part, to the fact that the elastic moduli scarcely depend
on the quality of the fiber-matrix interface, since the test involves
very low strains (Gonza
lez-Sa

nchez et al., 2014). The addition of
MAPE also has a limited effect on the values of st. The addition of
MAPE causes remarkable increases in st only in composites with
high fiber content. This is not the usual behavior in composites
made from virgin PE and cellulose, where MAPE is widely used as
coupling agent because of its recognized ability for improving the
chemical compatibility between the hydrophobic PE and the hy-
drophilic cellulose and, hence, the fiber-matrix adhesion at the
interface and the values of st.
In order to ascertain the reasons of the behavior of the eco-
composites obtained from recycled plastics, the morphology of
these materials was studied by SEM. Fig. 5 shows typical images of
fractured surfaces of non-coupled and MAPE-coupled eco-com-
posites. As shown in Fig. 5b and c, the increase of the MAPE content
results in an improved interfacial adhesion between the fibers and
the matrix, as well as a reduction of the length of the protruding
suggests that the interface withstood the stress until the fiber
breakage occurred. For non-coupled composites, Fig. 5a shows
some signs of compatibilization, since some fibers esuch as the one
pointed by an arrow-show a good adhesion to the matrix.
The compatibilization observed in eco-composites obtained
from RAP and rHDPE, usually not observed in composites obtained
from virgin PE, has been explained as a result of the presence of EVA
in the RAP. The polar acetate moiety of EVA enhances the fiber-
matrix chemical compatibility and promotes the dispersion and
wetting of the cellulose fibers. In fact, EVA has been used by La
Mantia and Morreale (2006) as an additive to overcome the poor
adhesion between cellulose and PE. Therefore, the observed effect
of MAPE can be related to the presence of EVA in the RAP, which
acts as coupling agent, thus explaining that only minor additional
increases in the values of the mechanical properties are observed
when MAPE is added. This hypothesis may also explain why the
positive effect of MAPE is observed only in the eco-composites with
high fiber contents, since higher fiber contents require higher ad-
ditions of coupling agent. This result confirms that the presence of
EVA in agricultural plastic wastes adds value towards their use in
the manufacture of composites with lignocellulosic materials.
Another factor that may contribute to explain the limited effect
of MAPE on the mechanical properties has been discussed in detail
in a previous work, where it has been shown that MAPE causes a
reduction of the average length of the cellulose fibers, which can
contribute to the reduction of the mechanical properties
(Gonz
alez-S
anchez et al., 2014). The breakage of the fibers during
the processing of the eco-composites can be explained as a result of
the strong fiber-matrix adhesion (including chemical bonds) ach-
ieved when MAPE is used, as it can be observed in Fig. 5c.
Table 1 also shows that, as might be expected, the fibers greatly
reduce the maximum elongation as well as the impact strength of
the polymers. The unreinforced 60/40 blends do not break in the
impact test, under the conditions used in this work. The cellulose
and coupling agent effects on the impact resistance could not be
studied because the standard deviations were very high in this test,
as shown in Table 1. The elongation decreases as the cellulose
content increases and the values appear to be slightly higher when
the coupling agent is used. The most important difference appears
in the unreinforced blends, whose elongation increases by more
than 27% with only 1.5 wt % of MAPE, which confirms that MAPE
can act as a plasticizing agent in this plastic.
Finally, Table 1 shows that the MFI greatly decreases as the fiber
content increases, which significantly complicates the process-
ability of these materials. It is important to note here that the
presence of MAPE can reduce, at least in part, this problem, because
it causes small increases of the MFI values. MAPE acts as lubricant
due its low molecular weight, with regard to that of the matrix.

Table 1
Properties of eco-composites obtained from the 60/40 RAP/rHDPE blend, coupling agent (MAPE) and waste cellulose fibers (WCF).

WCF (wt %) MAPE (wt %) Et (GPa) st (MPa) εt (%) Impact S. (kJ/m2) MFI (g/10 min)

0 0 0.33 (0.03) 13.71 (0.17) 268.2 (20.4) e 94.16 (2.02)

25 0.92 (0.05) 19.25 (0.58) 7.45 (0.74) 33.43 (5.37) 12.50 (2.66)
30 1.10 (0.02) 22.73 (0.78) 6.06 (0.30) 28.58 (12.37) 9.74 (1.24)
35 1.21 (0.03) 20.54 (0.46) 4.72 (0.55) 29.37 (15.92) 6.11 (0.85)
0 1.5 0.31 (0.02) 15.72 (0.51) 342.2 (37.7) e 93.86 (4.92)
25 0.96 (0.04) 20.56 (0.24) 7.93 (0.26) 32.13 (10.72) 12.77 (1.50)
30 1.07 (0.05) 23.02 (0.37) 6.21 (0.32) 36.95 (12.27) 10.15 (0.83)
35 1.23 (0.06) 23.21 (0.64) 5.38 (0.13) 24.96 (7.78) 6.66 (0.92)
0 3 0.32 (0.03) 15.60 (0.38) 342.3 (12.9) e 81.77 (1.75)
25 0.88 (0.04) 19.63 (0.59) 8.80 (0.57) 33.77 (4.56) 16.12 (1.89)
30 1.15 (0.08) 24.14 (0.28) 6.51 (0.23) 35.72 (17.32) 11.49 (1.11)
35 1.32 (0.06) 24.63 (0.61) 5.25 (0.32) 27.79 (11.07) 7.89 (0.76)

Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
6 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8
Fig. 5. SEM images of fracture surfaces of 35 wt% cellulose-reinforced RAP/rHDPE
composites (40 wt% of rHDPE in the matrix) with: a) No MAPE, b) 1.5 wt% of MAPE and
c) 3 wt% of MAPE.
3.3. Effects of rHDPE on the properties of the eco-composites
Specific strength and stiffness are very important indicators of
the structural performance of a material and, in many applications,
are the most critical engineering characteristics of the material
(Koronis et al., 2013). Previous results have shown that RAP has
good toughness and processability and that stiffness and strength
Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
are improved by using WCF as reinforcement (Gonza
lez-Sa
nchez
et al., 2014). A different way for improving the stiffness and
strength of the final recycled materials, without compromising the
toughness and the processability, has been tested in this work. The
blending of two or more immiscible polymers has been shown to
be, in selected cases, a very effective way for obtaining new mate-
rials with useful combinations of properties (Martins et al., 2009).
This pathway has been extensively studied with virgin resins, but
not with plastic wastes, although residues with very different
properties and characteristics are easily available. Following this
pathway, one of the main goals of this work has been to evaluate
the effect of blending RAP with a second recycled plastic, rHDPE,
whose major component, HDPE, is more rigid than the plastics
found in RAP, on the properties of the final eco-composites.
In order to study the effects of blending RAP with rHDPE, the
properties of the eco-composites obtained in this work from the 60/
40 blend have been compared to those of the corresponding eco-
composites prepared by using RAP alone as matrix, which have
been reported in a previous work (Gonza
lez-Sa

nchez et al., 2014).
These comparisons, all corresponding to eco-composites with
1.5 wt % of MAPE and 0.3 wt % of antioxidant, are given in Fig. 6.
From Fig. 6 it is seen that the incorporation of 40 wt % of rHDPE
in RAP causes significant increases in the elastic modulus of the
neat plastic and the eco-composites. The observed increases in the
tensile modulus are as high as 175% for the polymer and 47% for the
eco-composite with 30 wt % of WCF. Similarly, the incorporation of
rHDPE increases the tensile strength of the eco-composites, while
the impact strength does not undergo significant changes, consid-
ering the standard deviations. That is, the above results indicate
that the incorporation of rHDPE significantly increases the stiffness
and strength of the recycled materials without compromising the
toughness thereof. These are important results because, as
mentioned above, the strength, stiffness and toughness are key
parameters in the structural performance of the materials.
Fig. 6 also shows that incorporation of rHDPE causes pro-
nounced decreases in the MFI, which can be important for the in-
jection molding and the processability of these materials. However,
it is important to note that the decrease of MFI due to the intro-
duction of rHDPE is not observed when the mass fraction of WCF
reaches 0.35, that is, that the effect is only observed in composites
with low percentages of WCF, while eco-composites are commonly
used with the highest possible mass fraction of cellulose. Further-
more, as shown in Table 1, the MFI of the eco-composites obtained
from the blend of wastes increases as the MAPE content becomes
higher, so that the problems derived from the low MFI can be
corrected, at least partially, by increasing the percentage of
coupling agent.
4. Conclusions
In this work, a blend of a recycled agricultural plastic (RAP) and
post-consumer HDPE has been compounded with waste cellulose
fibers and coupling agent for obtaining different eco-composites.
The characterization of the blends indicates that they contain
LDPE and HDPE as major components, with minor but significant
amounts of EVA, PP, photo-stabilizer (and other additives) and
impurities. The use of rHDPE causes an important increase in the
melt viscosity of the blends, so it was decided to limit to 0.4 its mass
fraction in the blend.
The eco-composites show good properties even in the absence of
added coupling agent, due to the presence of the polar acetate
groups of EVA, which improves the physicochemical compatibility
between the polymeric matrix and the polar cellulose surface. The
incorporation of the cellulose fibers greatly increases the tensile
elastic modulus and the strength of the materials but decreases the
 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8
Fig. 6. Effects of the incorporation of rHDPE. White (Red in web version): WCF/RAP composites; gray (Green in web version): WCF/RAP/rHDPE composites (40 wt % of rHDPE in the
matrix).
impact strength, the maximum elongation and the MFI. The addition
of a maleated polyethylene as coupling agent improves the values of
tensile strength, elongation and MFI of the eco-composites.
The comparison between the properties of these eco-composites
and those of the corresponding ones made without rHDPE reveals
that the incorporation of the recovered HDPE causes significant im-
provements in tensile stiffness and strength. The MFI values decrease
but the detrimental effect of rHDPE is only significant at low cellulose
contents and can be reduced by using higher coupling agent contents.
The impact strength does not significantly change, so it can be
concluded that the incorporation of recovered HDPE allows obtain-
ing materials with improved balance between stiffness and tough-
ness, thus increasing the applications of the different wastes used in
this work and contributing to reduce their environmental impact.
Acknowledgments
The authors wish to gratefully acknowledge to the Ministerio de
Medio Ambiente of Spain for the financial support to this work
through the funds of the project MMA-A462/2007/2-02.7, and to
the Government of the Principality of Asturias for supporting Alvar
Martínez-Aguirre with a fellowship of its Science, Technology and
Innovation Plan.
References
Al-Oqla, F.M., Sapuan, S.M., 2014. Natural fiber reinforced polymer composites in
industrial applications: feasibility of date palm fibers for sustainable automo-
tive industry. J. Clean. Prod. 66, 347e354.
Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
7
Al-Salem, S.M., Lettieri, P., Baeyens, J., 2010. The valorization of plastic solid waste
(PSW) by primary to quaternary routes: from re-use to energy and chemicals.
Prog. Energy Combust. Sci. 36, 103e129.
Al-Salem, S.M., Evangelisti, S., Lettieri, P., 2014. Life cycle assessment of alternative
technologies for municipal solid waste and plastic solid waste management in
the Greater London area. Chem. Eng. J. 244, 391e402.
Alves, C., Ferr~ao, P.M.C., Silva, A.J., Reis, L.G., Freitas, M., Rodrigues, L.B., Alves, D.E.,
2010. Ecodesign of automotive components making use of natural jute fiber
composites. J. Clean. Prod. 18 (4), 313e327.
Bocken, N.M.P., Short, S.W., Rana, P., Evans, S., 2014. A literature and practice review
to develop sustainable business model archetypes. J. Clean. Prod. 65, 42e56.
Borja, Y., Rie, G., Lederer, K., 2006. Synthesis and characterization of polypropylene
reinforced with cellulose I and II fibers. J. Appl. Polym. Sci. 101, 364e369.
Briassoulis, D., Hiskakis, M., Babou, E., 2013. Technical specifications for mechanical
recycling of agricultural plastic waste. Waste Manag. 33, 1516e1530.
de la Orden, M.U., Gonza
lez-S
anchez, C., Gonza
lez-Quesada, M., Martínez
Urreaga, J., 2007. Novel polypropyleneecellulose composites using poly-
ethylenimine as coupling agent. Compos. Part A Appl. Sci. Manuf. 38,
2005e2012.
European Commission, DG ENV, 2014. http://ec.europa.eu/environment/waste/
(accessed 03.07.15.).
Faruk, O., Bledzki, A.J., Fink, H.-P., Sain, M., 2012. Biocomposites reinforced with
natural fibers: 2000e2010. Prog. Polym. Sci. 37, 1552e1596.
Fonseca, C.A., Harrison, I.R., 1998. An investigation of co-crystallization in LDPE/
HDPE blends using DSC and TREF. Thermochim. Acta 313, 37e41.
Fu, Q., Men, Y., Strobl, G., 2003. Understanding of the tensile deformation in HDPE/
LDPE blends based on their crystal structure and phase morphology. Polymer
44, 1927e1933.
Gattiglia, E., Turturro, A., Serra, A., Delfino, S., Tinnirello, A., 1993. Recycling of
plastics from urban solid wastes: comparison between blends from virgin and
recovered from wastes polymers. In: La Mantia, F.P. (Ed.), Recycling of Plastic
Materials. ChemTec, Toronto, pp. 39e57.
Gonza
lez-Sa
nchez, C., Gonz
alez-Quesada, M., de la Orden, M.U., Martínez
Urreaga, J., 2008. Comparison of the effects of polyethylenimine and maleated
polypropylene coupling agent onto the properties of cellulose-reinforced
polypropylene composites. J. Appl. Polym. Sci. 110, 2555e2562.
Gonza
lez-Sa
nchez, C., Martínez-Aguirre, A., Pe
rez-García, B., Martínez Urreaga, J., de
la Orden, M.U., Fonseca-Valero, C., 2014. Use of residual agricultural plastics and
8 J. Martínez Urreaga et al. / Journal of Cleaner Production xxx (2015) 1e8
cellulose fibers for obtaining sustainable eco-composites prevents waste gen-
eration. J. Clean. Prod. 83, 228e237.
Hopewell, J., Dvorak, R., Kosior, E., 2009. Plastics recycling: challenges and oppor-
tunities. Philos. Trans. R. Soc. Lond. B Biol. Sci. 364, 2115e2126.
Kazemi Najafi, S., 2013. Use of recycled plastics in wood plastic composites - a re-
view. Waste Manag. 33, 1898e1905.
Kitagawa, K., Ishiaku, U.S., Mizoguchi, M., Hamada, H., 2005. Bamboo-based eco-
composites and their potential applications. In: Mohanty, A.K., Misra, M.,
Drzal, L.T. (Eds.), Natural Fibers, Biopolymers, and Biocomposites. CRC-Taylor &
Francis, Boca Raton, pp. 392e393.
Koronis, G., Silva, A., Fontul, M., 2013. Green composites: a review of adequate
materials for automotive applications. Compos. Part B Eng. 44, 120e127.
La Mantia, F.P., Morreale, M., 2006. Mechanical properties of recycled polyethylene
ecocomposites filled with natural organic fillers. Polym. Eng. Sci. 46, 1131e1139.
La Rosa, A.D., Recca, G., Summerscales, J., Latteri, A., Cozzo, G., Cicala, G., 2014. Bio-
based versus traditional polymer composites. A life cycle assessment perspec-
tive. J. Clean. Prod. 74, 135e144.
Le Duigou, A., Baley, C., 2014. Coupled micromechanical analysis and life cycle
assessment as an integrated tool for natural fiber composites development.
J. Clean. Prod. 83, 61e69.
Li, T.Q., Wolcott, M.P., 2005. Rheology of wood plastics melt. Part 1. Capillary rhe-
ometry of HDPE filled with maple. Polym. Eng. Sci. 45, 549e559.
Martins, C.G., Larocca, N.M., Paul, D.R., Pessan, L.A., 2009. Nanocomposites formed
from polypropylene/EVA blends. Polymer 50, 1743e1754.
Please cite this article in press as: Martínez Urreaga, J., et al., Sustainable eco-composites obtained from agricultural and urban waste plastic
blends and residual cellulose fibers, Journal of Cleaner Production (2015), http://dx.doi.org/10.1016/j.jclepro.2015.06.001
Minick, J., Moet, A., Baer, E., 1995. Morphology of HDPE/LDPE blends with different
thermal histories. Polymer 36, 1923e1932.
Mohanty, A.K., Misra, M., Drzal, L.T., Selke, S.E., Harte, B.R., Hinrichsen, G., 2005.
Natural fibers, biopolymers, and biocomposites: an introduction. In:
Mohanty, A.K., Misra, M., Drzal, L.T. (Eds.), Natural Fibers, Biopolymers, and
Biocomposites. CRC-Taylor & Francis, Boca Raton, p. 27.
PlasticsEurope, 2014. Plastics e the Facts 2013. An Analysis of European Latest
Plastics Production, Demand and Waste Data. http://www.plasticseurope.org/
cust/documentrequest.aspx?DocID¼59108 (accessed 03.07.15.).

nchez-Soto, M., Rossa, A., Sa
Sa
nchez, A.J., Ga

mez-Pe

rez, J., 2008. Blends of HDPE
wastes: study of the properties. Waste Manag. 28, 2565e2573.
Scoponi, M., Cimmino, S., Kaci, M., 2000. Photo-stabilisation mechanism under
natural weathering and accelerated photo-oxidative conditions of LDPE films
for agricultural applications. Polymer 41, 7969e7980.
Wan Alwi, S.R., Manan, Z.A., Klemes, J.J., Huisingh, D., 2014. Sustainability engi-
neering for the future. J. Clean. Prod. 71, 1e10.
Wignall, G.D., Londono, D., Lin, S., Alamo, R.G., Galante, M.J., Mandelkern, L., 1995.
Morphology of blends of linear and long-chain-branched polyethylenes in the
solid state: a Study by SANS, SAXS, and DSC. Macromolecules 28, 3156e3167.
Yam, R.C.M., Mak, D.M.T., 2014. A cleaner production of rice husk-blended poly-
propylene eco-composite by gas-assisted injection moulding. J. Clean. Prod. 67,
277e284.