Polymer Degradation and Stability 97 (2012) 1654e1661

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Polymer Degradation and Stability

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

Experimental tests and technical characteristics of regenerated films

from agricultural plastics
Pietro Picuno a, Carmela Sica a, Rocco Laviano b, Aleksandra Dimitrijevi

c c, *,
Giacomo Scarascia-Mugnozza d
a
University of Basilicata, DITEC Department, Potenza, Italy
b
Bari University “Aldo Moro”, Earth and Environmental Sciences Department, Bari, Italy
c
University of Belgrade, Faculty of Agriculture, Department for Agricultural Engineering, Nemanjina 6, 11080 Belgrade, Serbia
d
Bari University “Aldo Moro”, Agricultural and Environmental Science Department, Bari, Italy

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

Article history: Current agricultural practices require the use of large quantities of plastics, which contribute to
Received 6 April 2012 a significant increase of the quantity and quality of agricultural production, but also require high
Received in revised form quantities of plastic waste to be disposed in such way that will not have a negative effect on the land-
12 June 2012
scape and the agro-ecosystem. In this paper the results of an experimental investigation of the possi-
Accepted 18 June 2012
bilities of producing new regenerated plastic films through mechanical recycling, from post-consume
Available online 28 June 2012
agricultural plastic films are analysed. Six recycled films, made from agricultural low tunnel and
greenhouse covering films as well as from HDPE bags for agrochemical packaging, have been extruded
Keywords:
Agricultural plastic waste
producing films of different thickness. These regenerated films were characterized by means of
Mechanical recycling mechanical and spectrometric tests and SEM þ EDS analysis. The obtained results show that without
Plastic films adding any additives into the blends good mechanical and spectral properties can be achieved by mixing
Plastic film mechanical properties the greenhouse and low tunnel recycled plastic film coverings.
Plastic film radiometric properties Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction Apart from their diverse use and contribution to a significant

Plastic materials have a wide range usage due to their versatile
properties such as light weight, resistance to break, low cost, ease of
manufacture, fabrication and shaping [1]. Concerning the agricul-
tural production, especially horticulture, an extensive and steadily
expanding use of plastic films is reported world-wide since the
middle of the last century. Some of the reported benefits of using
plastic materials in agricultural fields result from increased yields,
earlier harvests, less reliance on herbicides and pesticides, frost
protection and water conservation through the reduced irrigation
and water consumption [2e4]. It has also provided a more efficient
use of farm land, higher quality of crops and a resulting healthier
environment. Furthermore, for example in arid regions, plastics
piping/drainage systems can cut irrigation costs by one to two-
thirds while as much as doubling crop yield. In particular, the
market of plastics used for these purposes in Europe involves
hundreds of thousands of hectares and hundreds of thousands of
tons of plastic films per year.
* Corresponding author. Tel.: þ381 112194606, þ381 63268202 (mobile);
fax: þ 381 113163317.
E-mail address: saskad@agrif.bg.ac.rs (A. Dimitrijevi

c).
increase in productivity the use of plastics causes high quantities
of post-consume material that need to be disposed in such way
that will not cause negative effect on the landscape and agro-
ecosystem [5]. Current intensive and semi-intensive agricultural
practices require the use of large quantities of plastics [6]; the
consumption of plastic materials used throughout Europe for
agricultural applications reached 615,000 t in 2004 [7].
Most recent data suggest that agriculture and horticulture are
responsible for the consumption of, approximately 1 < 500,000
t/year of all polymers in Europe. Consumption of greenhouse and
low tunnel covering films in Europe amounts to 72,000 and
75,000 t/year, respectively. In Italy, with the respect to an average
annual consumption of more than 350,000 t of agricultural
plastic, it is estimated a corresponding flow of post-consume
material of about 200,000 t/year. Approximately, 55% of this
quantity [8] comes from protected cultivation (greenhouse clad-
dings, low tunnels, soil mulching, vineyards nets, etc.). So far,
there is no specific legal framework in Europe to ensure and
environmentally friendly, economically feasible and socially
accepted disposal system for agricultural plastic waste [9].
LabelAgriWaste [10] developed a proposal for improvement of the
European Legislation on solid waste (Revised Waste Framework

0141-3910/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.06.024
 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661
Directive 2008/98/EC) in a way of incorporating the proposed
labelling scheme for agricultural plastic waste [11].
The intensive and expanding use of plastics in agriculture results
in increased accumulation of plastic waste in rural areas. A large
part of agricultural plastic waste may be recycled, especially the
greenhouse films, silage films and fertilizer sacks, pipes and other
plastic products. There are many studies that consider the
mechanical recycling an appropriate system for recovery of post
consumption agricultural plastic film [12e16].
Recycling and reusing of different plastic materials is one of the
processes to reduce the environmental pollution problem. One of
the fundamental goals of recycling is to improve different proper-
ties of the recycled plastics [1]. The properties can be improved
substantially if composites are made by combining plastic waste
materials with cellulosic materials. Solution blending involves the
use of solvents which are not eco-friendly. Melt blending suffers
from some disadvantages like stress development, temperature etc.
There is not only a lot of focus on the recycling of post-consumer
solid waste, but also the plastics industry has recognized the need to
recycle industrial waste since all processing techniques produce some
residues such as off-spec resin, trims of moulded parts, or poor quality
parts [17]. The recycling of plastic films of agricultural origin is a tech-
nique of low environmental impact, well appreciated by the public
opinion, because it doesn’t produce harmful substances as may happen
during other disposal techniques, e.g. incineration [18]. It may also lead
to interesting advantages, from a technical and economical point of
view, through the creation of new products, the improvement of those
existing and the development of new applications, with decreasing
costs of the whole process if mechanical recycling of heterogeneous
plastic material is possible, where the need to separate different
polymers is avoided. The characteristics of the recycled material
depend on those of the virgin material, on the level of dirtiness of the
post-consume (used) material and of the recycling process itself.
Amin [19] discussed ways of improving the properties of
greenhouse covering by introducing a three layer film whose
middle layer is a recycled LDPE film. Research presented by Lima
[20] discusses the philosophy of using two waste materials to
produce a newer material presenting comparable properties with
those of the conventional non-renewable materials which was
suggested will go long way not only in mitigating the environ-
mental problem but also in providing additional employment
through collection and transportation of such materials.
The aim of this paper is to present some research results in the
area of plastic materials mechanical recycling. The paper gives the
basic mechanical and spectral characteristics of the new materials
obtained from low tunnel and greenhouse plastic film coverings.
2. Materials and methods
Plastic samples that were tested and analysed were obtained
from plastic films used as cladding materials for low tunnels and
greenhouses in different farms in Huelva and Almeria regions
(Spain). These agricultural plastic films were collected and recycled
in form of granules by the INSERPLASA S.A. Company (Spain). After
the granulation the Company extruded four transparent films
(F1eF4) different in their mixtures:
- F1 e recycled film obtained from regenerated granules of
greenhouse film (50%) and low tunnel film (50%);
- F2 e recycled film obtained from regenerated granules of
greenhouse film (75%) and low tunnel film (25%);
- F3 e recycled film obtained from regenerated granules of
greenhouse film (25%) and low tunnel film (75%);
- F4 e obtained as a mixture F1 (25%) þ F2 (25%) þ F3
(25%) þ HDPE, from agrochemical packaging (25%).
1655
PATI SpA Company (Italy) has extruded two other materials,
densified material (Fd5) and granulated material (Fg6) obtained
from regenerated granules of greenhouse and tunnel films. Densi-
fied material (Fd5) was obtained from pellet extrusion at
180e200  C. The pellets were of sufficiently small dimensions to be
fed to the extruder hopper. The other material (Fg6) was obtained
from the densified resin that was cooled to 70e80  C and re-
extruded. In this way granulated material was obtained.
The materials analysed in this work were collected and recycled,
in case of low tunnels, after one production season, and, in case of
greenhouse coverings, after two seasons. In order to define the
mechanical properties of new recycled materials two virgin mate-
rials were used for comparing the results. Virgin materials were
obtained from the same locations as materials for recycling. The
difference of the thickness was considered when these recycled
films were analysed and compared to the virgin one. Materials F1,
F2, F3 and F4 (respectively 40, 40, 40 and 30 mm) were compared
with a virgin LDPE film (T1), 50 mm thick, while materials Fd5 and
Fg6 (respectively 150 and 60 mm) were compared with a virgin EVA
film (T2), 160 mm thick.
All recycled films were tested by means of mechanical tests and
spectral and scanning electron microscopy (SEM) analysis.
Mechanical tests were carried out in the Laboratory of Material
Testing of the Technical-economic Department of the University of
Basilicata, Italy. For each material n.10 specimens were cut. Five
specimens were taken along the parallel direction of the extrusion
and five specimens in the transverse direction. The tensile tests
were carried out using a computerized universal machine Galda-
bini PMA 10 according to the Italian UNI 8422 Standard [21], at
constant deformation velocity of 200 mm min1. Each test con-
cerned 10 specimens, so expressing the results in terms of average
value and bilateral confidence interval with 95% probability [22].
The results obtained from tensile tests are reported in terms of
maximum resistance (smax) expressed in [MPa], percentage elon-
gation (ε) and percentage elongation at break (εbr) expressed in [%].
The spectral analysis, aimed to the definition of the optical
properties of the six regenerated films, was performed in the
Laboratory of Spectro-radiometric Analysis of the DISAAT Depart-
ment of the University of Bari e Italy, using spectrophotometers
PerkineElmer UVeVIS and FT-IR 1760X [23]. The transmittance to
radiation in the wavelength range from 190 nm to 25,000 nm was
determined. An integrating sphere was used to evaluate the diffuse
fraction of the transmitted radiation in the PAR range.
SEM analysis was carried out at the University of Bari at the
Earth and Environmental Sciences Department. The materials after
recycling were characterized by a SEM of LEO, model EVO50XVP.
The samples were fixed on aluminium stubs with colloidal graphite
and then sputtered with a 30 nm thick carbon film. Investigations
on the samples were carried out with both secondary electrons (SE)
and back-scattered electrons (BSE).
Semi-quantitative analyses of the elemental composition of
present minerals were obtained using a Si(Li) Pentafet ED Oxford-
Inca detector equipped with an Atmosphere Thin Window 2Ó.
Operating conditions of the SEM were: 15 kV the accelerating
potential, 500 pA the probe current and 20.0 mm the working
distance.
3. Results and discussion
3.1. Mechanical properties of the recycled materials
The recycling of homogenous polymers is a relatively easy
challenge only when their structure is preserved and no significant
degradation took place either during the lifetime or the recycling
[15]. Agricultural covering and mulching films are exposed to
1656 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661

natural weathering that influences their mechanical, chemical and

optical properties in different ways leading to significant thermal,
chemical and mechanical degradation [3]. Level of the degradation
influences their post-recycling characteristic and thus determines
their future applications [24].
The results of the tensile tests, obtained for the regenerated
samples, show that there are differences in terms of maximum
resistance (smax) and percentage elongation at break (εbr). When
compared to the LDPE film, recycled samples (Table 1) show similar
and higher values of the maximum resistance. According to EN ISO
527-3 standard [25] that deals with mulching films, all these films
except F3 have appropriate characteristics in terms of maximum
resistance (smax  20 MPa). The highest value was observed for the
F2 material and the lowest for the F3 material. The results reported
by Ma and La Mantia [24] stated that with the recycled LDPE worse
characteristics are to be expected when compared to the virgin
LDPE. They reported 15.2 MPa maximum resistance for the virgin
LDPE and 11.5 MPa for the recycled LDPE.
The F1 and F3 samples show similar values for maximum
resistance regardless of the tension direction, while there are some
differences regarding F2 and F4 samples showing higher values in
the direction transverse to tension direction (Fig. 1).
Concerning the percentage elongation at break there was an
obvious worsening of the material properties. All the materials
show lower values compared to the virgin LDPE. Only material F2
can fulfil the standard demands [25] for the good quality mulching
film (εbr  300%). Mechanical properties of the recycled materials
depend on those of the virgin material [3] and the level of its
degradation after the usage correlated with the ageing, caused by
sun UV radiation exposure, and the conditions of material usage,
like exposure to agrochemicals, mechanical stress, etc. The
mechanical degradation of plastic films can affect the recyclability
of the materials as it is directly related to the chemical-structural
changes of the polymer.
Materials F2 and F4 show a certain inhomogeneity of results
when tensioned in the parallel and transverse direction (Fig. 1).
Higher percentage of elongation was observed in the transverse Fig. 1. Strainestress curves for F1, F2, F3 and F4 material in the parallel (TP) and
direction for both materials. The reason can be found in the inho- transverse (TT) direction to the extrusion.
mogeneity of the materials themselves. Based on the mechanical
test results it can be said that a combination of 75% of greenhouse
properties compared to tension in direction parallel to extrusion
coverings and 25% low tunnel films, after recycling can give
(Fig. 2).
a material that fulfils the standard demands for a good mulching
Tzankova Dintcheva et al. [26] and Tzankova Dintcheva et al.
plastic film. If compared with the standard mechanical properties
[27] reported the more suitable mix, obtained with about 75% LDPE
of mulching materials [25] it can be concluded that material F2 can
(low density polyethylene), 15% LLDPE (linear low density poly-
be treated as a good quality material for the normal mulching film.
ethylene) and 10% EVA (ethylene-vinyl acetate copolymer),
The other group of materials that were compared to virgin EVA
revealed good characteristics in terms of flexibility at low temper-
greenhouse covering showed different mechanical properties. The
atures, resistance to degradation, and mechanical characteristics at
values of the maximum resistance varied from15.4 N mm2 (Fd5) to
high temperatures. Their analysis of virgin material influence on
18.7 N mm2 (Fg6) and were lower than the value obtained for the
the properties of new recycled films was analysed formulating
virgin EVA material as well as for the materials from the previous
different blends of virgin and used materials. Other studies showed
group (Table 2). Material Fg6 had higher maximum resistance
that the addition of different percentages of VA to LDPE increases
when tensioned in transverse direction while values for Fd5
maximum strength resistance, hardness and resistance to lacera-
materials were similar in both directions of extrusion.
tion of the recycled film and improves its radiometric characteris-
The values of the elongation at break of Fd5 and Fg6 samples
tics [28].
were similar and very low. The tests show that both materials
According to the EN ISO 527-3 standard [25] it can be concluded
tensioned in transverse direction present better deformability
that material Fg6 can be considered as a covering material that
fulfils the standard characteristics of a covering “normal film”
Table 1
Mechanical properties of F1, F2, F3 and F4 recycled materials.
Table 2
Material Thickness (mm) smax (MPa) εbr (%) Mechanical properties of the Fd5 and Fg6 recycled materials.
F1 40 20.60  2.75 246.75  25.58
F2 40 35.71  4.45 310.51  36.77 Material Thickness (mm) smax (MPa) εbr (%)
F3 40 12.54  1.23 261.95  37.46 Fd5 150 15.41  0.96 191.20  25.37
F4 30 29.93  3.66 247.69  67.00 Fg6 70 18.72  2.51 190.87  44.34
T1 50 21.74  1.23 439.90  139.32 T2 160 34.54  11.30 536.44  7.56
 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661 1657

Fig. 2. Strainestress curves for Fd5 and Fg6 material in the parallel (TP) and transverse
(TT) direction to the extrusion.

Fig. 3. Spectral transmittance of F1, F2, F3 and F4 plastic films (200e25,000 nm).

because its maximum resistance is higher than 17 MPa and its

elongation at break is higher than 180%. material. The highest transmittance was observed for F1 (76.4%)
and the lowest for the Fd5 material (37.9%).
3.2. Spectral properties of the new materials The more transparent the film is to NIR, the more heat will reach
the protected cultivation and the soil. In the case of recycled films
All the regenerated films showed quite similar spectral charac- that were compared with the LDPE, it can be seen that all materials
teristics (Table 3). Analysing the behaviour of the films in the solar show the same “pattern” in transmitting NIR and that all the results
wavelength range, and specifically in the PAR, it is possible to note are included in the range 81%e85% except for Fd5 (77.2%) that is
that materials F1, F2 and F3 had a transmittance higher than 80% also much more diffusive, 37% in the NIR and 39% in the solar wave-
while F4, Fd5 and Fd6 films were characterized by PAR trans- length range, compared to F1eF4 and Fg6 samples.
mittance less than 80%. Lower transmittance of F4 is the result of The greenhouse effect of the protected cultivation technique
the fact that this material in its composition had 25% of HDPE from depends on the impermeability of the covering materials to long-
agrochemical packaging which is not transparent in the PAR. On the wave infrared radiation. As is well known, not all wave-lengths of
other hand, Fd5 had significantly higher thickness compared to the the infrared (IR) spectrum are equally relevant from the thermal
other samples, contributing to the worsening of the PAR point of view, since there are “atmospheric windows” in which the
transmittance. IR radiation emitted by the Earth preferentially escapes; one of
All the tested materials show a high UV transmittance which is these windows is located between 8 and 13 mm [28]. In the wave
related to the potential photo-degradation of the polymer by range of 3000e25,000 nm F1, F2, F3 and F4 samples show similar
sunlight. This characteristic can be appropriate if the F1, F2, F3 and transmittance patterns up to 15,000 nm after this value the
F4 materials are going to be used as mulching films (with carbon patterns are slightly different (Fig. 3). The highest transmittance
black additives), while it could lead to the ageing and degradation value in the long-wave IR range was observed for F2 (78.4%)
of the film during its use, if no anti-ageing additives are used in the throughout all the range and the lowest for F1 (63.2%). Concerning
the fact that material F2 had a content made of 75% of greenhouse
covering, it was expected to have a lower transmittance in the long-
Table 3
Results of the spectral analysis of the recycled materials. wave infrared radiation. In case of Fd5 and Fg6 samples, it can be
seen (Fig. 4) that the lower transmittance was observed for the Fd5
Wave length Measured parameter Material
material (24%).
range
F1 F2 F3 F4 Fd5 Fg6 Therefore it can be stated that in the long IR wavelength range,
Solar Transmission Total (%) 84.7 82.8 84.0 79.1 72.7 80.0 only the Fd5 film showed a low value while all other films were
200e2500 nm Direct (%) 59.4 59.6 60.2 54.1 33.2 45.7 characterized by significantly higher transmittance values [29] than
Diffuse (%) 25.3 23.2 23.9 25.0 39.5 34.3
the optimal value of a greenhouse covering films (s ¼ 0.35e0.40).
Reflection 8.0 8.6 8.0 11.3 7.9 7.6
PAR Transmission Total (%) 84.1 81.5 83.2 76.3 69.2 77.4 From the spectral analysis it can be seen that, with reference to
400e700 nm Direct (%) 51.7 50.1 52.1 42.2 26.1 36.8 the recycled materials composition and that the mixtures were
Diffuse (%) 32.4 31.4 31.1 34.1 43.1 40.6 made partially from greenhouse coverings, it has been expected
Reflection 8.4 9.2 8.4 12.7 8.3 7.9 that recycled materials could contain some percentage of vinyl-
Solar IR Transmission Total (%) 85.6 84.3 85.1 81.9 77.2 83.5
700e2500 nm Direct (%) 66.7 68.5 67.8 65.1 40.1 54.2
acetate (VA). According to the Italian Standard UNI ISO 8985 [30],
Diffuse (%) 18.9 15.8 17.3 16.8 37.2 29.3 it is possible to calculate the material IR absorbance based on its IR
Reflection 7.6 8.1 7.5 10.1 7.6 7.4 transmittance. Since samples F1eF4 had a thickness less than
UV Transmission Total (%) 76.4 74.8 74.7 67.1 37.9 53.6 50 mm, their content of VA was negligible while for the Fd5 material
280e380 nm Direct (%) 38.4 36.1 38.4 29.3 11.8 21.1
was 7.44% and for Fg6 6.44%. It is evident that the disposed plastic
Diffuse (%) 38.0 38.6 36.3 37.8 26.2 32.5
Reflection 9.9 10.1 9.9 11.0 7.9 8.6 materials classification prior the recycling process is of high
Long-wave IR Transmission Total (%) importance and that great attention should be taken when forming
7500e12500 nm Direct (%) 63.2 78.4 64.9 73.3 24.1 49.6 blends. Serranti and Bonifazi [31] stated that no matter how effi-
Diffuse (%) cient the recycling scheme is, sorting is the most important step in
Reflection 9.7 5.1 12.3 8.7 4.0 6.3
recycling loop. A good system of material traceability should be
1658 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661

Fig. 4. Spectral transmittance of Fd5 and Fg6 plastic films (200e25,000 nm).

introduced into the recycling management centres. Briassoulis et al.

[11] proposed the Labelling scheme for APW in Europe and stated
that traceability represents a key technical component that can
provide quality assurance of material from the plastic converters
level and the suppliers to the farmers and the collection area and
final disposal.

3.3. SEM analysis of new recycled materials

Back-Scattered Electrons (BSE) analysis was used to provide

information about the distribution of different elements (or
minerals) in the samples while Secondary Electron (SE) analysis
was used for analysing topography (or surface morphology) of
materials.
SEM analysis with the SE showed that all materials are
homogenous except materials F1 (Fig. 5 and Fig. 6). The damages
that can be seen on the figure are mechanical and are not caused by
the chemical composition of the sample. Considering that all
materials were subjected to the same recycling process, the damage
was not done during the recycling. The reasons can be searched in
the post-harvesting procedures of cleaning and storage.
Previous research on chemical properties of recycled agricul-
tural plastic materials shows that LDPE recovered from green-
houses contains oxygenated groups as a result of photooxidation,
crosslinks, additives and stabilizers [14]. The presence of oxygen-
ated groups can modify the solidification behaviour and also
crystallization.
Back-scattered electron analysis showed that all materials were
rich in single elements (or oxides) like Zn and Fe as well as in
minerals like rutile (TiO2), calcite (CaCO3), quartz (SiO2), feldspars
and kaolinite (Al2Si2O5(OH)4). The analysis showed that all mate-
rials were also rich in chlorines such as potassium chloride (sylvite,
KCl) and sodium chloride (halite, NaCl). Typical appearance of
sylvite was found to be as on Fig. 7. It was found like a group of
square shapes on the material surface. It appeared that sylvite was
starting to destroy film by making the holes in film around itself. In
this way mechanical properties of the material will soon been
worsened. The origin of the halite and sylvite can be from the air
pollution.
Presence of rutile can be related to the additives based on tita-
nium that were used during production of virgin materials since
pigments are used extensively in plastics for their UV resistant
properties where they act as a UV absorber, efficiently transforming
destructive UV light energy into heat. It was found in all samples
but in lower quantities for F3 and Fd5 materials. Presence of zinc
and aluminium can be explained by the fact that these can be found
in additives for film colouring.
Fig. 5. Surface of the F1 sample (SE images).
Calcite is the main constituent of sedimentary rocks such as
limestone and calcarenite much of which is formed from chemical
precipitation in sea environment and/or from the shells of dead
marine organisms. Calcite is also abundant in other sedimentary
rocks such as clayey deposits. Since plastic materials were collected
in the regions near sedimentary rocks the presence of calcite in
every sample can be easily explained.
Quartz is the second-most-abundant mineral in the Earth’s
continental crust, after feldspar minerals. Because of its resistance
to weathering it is very common in stream sediments and in
residual soils. Quartz could remain on the material after the
cleaning and washing or can originate from some additives for
improvement of optical properties of the virgin materials. Kaolinite
is one of the most common clay minerals. Kaolinite is used in
ceramics, medicine, coated paper, as a food additive in toothpaste,
as a light diffusing material. It is also used in paint to extend tita-
nium dioxide (TiO2) and modify gloss levels. In this way the pres-
ence of kaolinite can be justified by kaolinite being the additive or
kaolinite being the residue on the film before recycling. Muscovite
(KAl2(AlSi3O10)(F,OH)2) belongs to the mica group of phyllosilicate
minerals and it is also a very common mineral of sedimentary and
igneous rocks. It was found in F1, Fd5 and Fg6 materials.
Feldspar minerals were very common for all the samples. Albite
(NaAlSi3O8) and potassium feldspar (KAlSi3O8) appeared in all samples
while anortite (CaAl2Si2O8) was characteristic only for the F2 sample.
 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661
Fig. 6. Surface of the F2, F3 and F4 samples (SE images).
Gypsum (CaSO4*2H2O) appeared in all the samples except Fd5.
Gypsum is a mineral that prevalently outcrops, with thick and
extensive evaporate beds, in sedimentary rocks. Gypsum deposits
occur from deposition in lake and sea water, as well as in hot
springs, from volcanic vapours, and sulfate solutions in vein
geologic structures. It is often associated with halides and sulfur
minerals. Halite was found in all the samples but pure sulfur was
found in F1 and F2 materials. Its presence in the samples could
1659
Fig. 7. SEM pictures for KCl displacement pattern in the F2 (SE image) and F3 samples
(left: SE image; right: BSE image).
indicate the oxidizing conditions [13]. Dolomite (CaMg(CO3)2) was
found in all samples. Presence of dolomite can be explained by the
fact that in horticulture, dolomite and dolomitic limestone are
added to soils and soilless potting mixes to lower their acidity and
as a magnesium source. Sphalerite ((Zn,Fe)S) was also present, in
very small quantities, in all the samples except F1 and Fd5.
All materials except F1 had traces of lead and material F3 had
combination of lead and chromium. Materials Fd5 and Fg6 had
antimony in traces. One of the applications of antimony is as
a catalyst for the production of the polymer poly(ethylene tere-
phthalate) (PET) and as a pigment for glass. Materials F4 and Fd5
had the barite. Talc (Mg3Si4O10(OH)2) was found in materials F3 and
F4. Talc is used in many industries such as paper making, plastic,
paint and coatings, rubber, food, electric cable, pharmaceuticals,
cosmetics, ceramics, etc. If it was used as additive in film production
it will appear in all the samples.
F4 material was different from all the other having the traces of
nickel. Material F3 was different from all the others having the
cadmium and selenium traces. F1 was the only material having
magnesium. At the same time F1 showed traces of technetium but
this is very unusual because it has a lower atomic number element
without any stable isotopes. Nearly all technetium is produced
synthetically and only minute amounts are found in nature.
It can be seen that there is no perfect pattern of chemical
composition and that there are no two identical samples but certain
1660 P. Picuno et al. / Polymer Degradation and Stability 97 (2012) 1654e1661
similarity can be observed for the group of materials F3eFg6. All
materials in this group, if compared to F1 and F2, do not have
aluminium, sulfur, magnesium, cuprum, technetium, cadmium and
calcium and potassium feldspar.
Tzankova Dintcheva et al. [26], when comparing the results of
the chemical analysis and of the mechanical tests on specimens of
recycled films with those obtained in the virgin material, concluded
that the recycled material can be used again in a lot of applications
even if its optical characteristics decrease with the number of the
extrusive passages, especially due to oxidative degradation.
Mechanical characteristics, instead, even worse than the virgin
material, remain relatively good after a lot of extrusions. The
addition of suitable stabilizers before each extrusion during the
recycling process appeared anyway essential in order to obtain
improved properties [27].
The final properties of the new recycled material depend on the
amount of degraded polymer but mainly on the extent of degrada-
tion. When the degradation of the polymer is limited, good prop-
erties can be achieved, but if the degradative effects are more
pronounced, there is a general worsening of all the properties [3,13].
The degradation effects are connected to the applied production
technology (plant protection chemicals, fertilizers, type of fertil-
izers, ways of application etc.), production location (micro climatic
conditions, air and water compositions) and conditions of materials
storage before recycling. Further chemical analysis of the samples
can give some results that can help in improving the materials
characteristics and the whole recycling process and management
scheme by describing the conditions of collecting, storage and
preparation of the materials that are supposed to be recycled.
4. Conclusions
The strategic contribution of plastic materials to the develop-
ment of the agricultural sector is testified by their increasing use,
stimulated by a constant research of new polymers and blends by
the chemical industry, in protected cultivation, pasteurization of
soil, irrigation and drainage, packaging during harvesting, trans-
port, storage and sale of agricultural products. The solution of the
problem of agricultural plastic waste passes through the research of
new applications of the recycled material. One of the most inter-
esting ways appears to be the re-utilization of the agricultural
wastes in the same sector, through the realization of cheap and
effective products able to improve agricultural production.
In this paper six recycled materials were tested for mechanical and
spectral properties. Results show that without adding any additives
materials can obtain satisfactory mechanical properties if they are
extruded from mixture that consists of 75% of greenhouse covering
materials and 25% low tunnel coverings. Good mechanical properties
were also observed with material extruded in higher thickness when
combination of 25% of greenhouse covering and 75% low tunnel
covering was used. Spectral analysis revealed that all the tested
samples, except F4 and Fd5, show a visible light transmittance higher
than 80%. It can be concluded that good PAR transmittance can’t be
expected in the case where HDPE from agrochemical packaging is
added to the blends for recycling. F1 and F2 samples show good
properties for being considered as thermal diffusion film, according to
the EN 13206 standard. It can be concluded that with addition of
adequate additives these recycled material could find their imple-
mentation in horticulture as mulching or covering materials.
SEM analysis showed that materials were different in their
chemical composition but that all were rich in minerals, oxides and
chlorides that can influence the worsening of materials properties.
The origin of chlorides and some minerals is mostly from the air.
Kaolinite and Quartz indicate material contamination by the soil
before recycling. In this way it can be concluded that great attention
must be paid to collecting, classification, cleaning and storage of
collected plastic materials since this can influence final technical
properties of materials.
Mechanical recycling can represent the simplest way of
managing plastic waste and, at the same time, obtaining new
plastic materials that can be re-used in the agricultural sector.
Further investigation should be made on blends optimization and
on improving the spectral properties of new recycled materials.
Acknowledgement
The Contribution to programming and executing this research is
equally shared between the Authors. The Authors wish to thank Mr.
Cosimo Marano and Mr. Michele Cosmo, laboratory technicians,
respectively for the cooperation during the mechanical and spectral
tests. In the name of the A. Dimitrijevi
c, we wish to thank the
Ministry of Education and Science, Republic of Serbia, for funding
her post-doc research at DITEC Department at Basilicata University
in Italy (Grant no. 451-03-151/2011-02).
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