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201500156 |9
Summary: Plastic films used to make market bags are based on polymers such as
polyethylene, polystyrene and polypropylene. These materials require a long time
to degrade in the environment. Alternative technologies have been developed to
reduce the degradation time and the impact on the environment caused by
the conventional polymer materials, using pro-degrading additives or by the
development of biodegradable polymers. In Brazil, some city’s laws require the use of
biodegradable material in the production of market bags, but the absence of specific
surveillance policies makes their chemical composition unknown. The plastic bags
didn’t show the expected environmental behavior by the manufactures, so it is
important to understand the reasons why they are not biodegradable in Brazilian
landfills. In this paper, 7 samples that were obtained from a trading company and
commercial market of Belo Horizonte were analyzed. The samples were characterized
by biodegradable analysis, XRF, FTIR, SEM and TGA/DTA, which allowed the
identification and evaluation of the thermal behavior of the material in an inert and
oxidizing atmosphere. The results showed that plastic bags were composed by a
mixture of PLA and PBAT, with possible presence of TPS and titanium and calcium
fillers. All samples presented low biodegradability in compostable environment.
conventional polymers, based in the addition Almost all Brazilian plastic waste is
of pro-degrading additives, which allow a discarded in landfills that don’t have an
photo-oxidation mechanism.[4,5] The oxo- ideal environment to degrade it. Actually,
biodegradable polymers are conventional there isn’t a standardization for bags’
polymers with additives based in transition composition, and as a consequence, the
metals, that break the structure of polymeric biodegradable material that composes bags
chain in presence of light and oxygen, doesn’t degrade or biodegrade as expected
allowing the oxidation mechanism.[6] PBAT when discarded in a compostable environ-
presents mechanical properties similar to ment. In the other hand, there is a kind of
the ones that low density polyethylene has bag that is 50% composed by high density
and it is known as Ecoflex, a commercial polyethylene (HDPE) and 50% composed
biopolymer. Ecovio is a blend of PLA and by biodegradable material, according to
PBAT, and both Ecoflex and Ecovio are the producer.
produced by BASF.[7] Ecovio presents The present work’s goal is to identify the
characteristics similar to olefins in biode- composition of some commercial plastic
gradable material.[8,9] PBAT and TPS have bags composed only by biodegradable
received more attention as a composite due material and to understand why they don’t
to concerns about solid waste disposal, and degrade or biodegrade as expected. For this
also, TPS presents a hydrophilic behavior study, some thermal analysis in inert and
that favors the hydrolysis process during oxidant atmosphere were done, to under-
the biodegradation.[10] stand the influence of oxygen presence;
According to ASTM- D883-99 standard some physical and chemical analysis were
degradable plastic material is “a plastic also done, to verify the material composi-
designed to undergo a significant change in tion, while respirometry tests were used
its chemical structure under specific envi- to evaluate the behavior of the samples.
ronmental circumstances, resulting in loss of With the results of the characterization of
some properties” and biodegradable plastic samples is intended to understand why
is “a degradable plastic whose degradation the plastic bags don’t show the expected
results from the action of naturally occur- behavior and, then, propose solutions to
ring microorganisms such as fungi, bacteria this problem.
and algae”. The biodegradable behavior
of a material can be quantified by respiro-
metric rates methodology, according to the Experimental Section
NBR14283-1999 standard, which permits
to quantify the biodegradation of CO2 According to manufacturers, the oxo-
produced in a specific period.[11,12] degradable bags were composed by HDPE
Minas Gerais state’s, Brazil, MG 21.412/ and pro-degrading additives and they were
2014 law sets standards and restricts the completely degraded in 18 months. The
available market plastic bags in countries biodegradable bag may be produced by
where there is selective collect in compost- fermentation or a synthetic process, and
ing plants. In other words, the plastic bags it is completely biodegraded in approxi-
must be cross out in landfill sites, according mately 120 days.[13] The identification of
to ASTM-D883-99, about biodegradable these polymers allows us to know if they
materials.[11] However, despite the legal present a biodegradable behavior, accord-
requirements about the use of biodegrad- ing to the law. The identification study of
able bags, there is no guarantee about the the samples’ composition was performed by
polymeric material used. In first stage of thermal analysis in inert and oxidant atmo-
law (2011) only biodegradable material sphere, solubility tests, Scanning Electron
should be used to produce plastic bags. Microscopy (SEM) and X-Ray Fluorescence
From 2014, bags needed to be biodegrad- (XRF). The Thermogravimetric Analysis
able but their composition was not defined. (TGA) and the Difference Temperature
Analysis (DTA) show changes in physical presented an insoluble residue. All samples
and chemical properties as a function of were soluble in xylene at 80 C, but B100L
temperature. The Fourier Transform Infra- presented the same insoluble residue.
red Spectroscopy (FTIR) allows the identi- According to fabricant, OXI bag is formed
fication of the functional groups of the by HDPE chains and it was soluble in
samples, which were confirmed by solubility xylene under heating. That occurs because
tests. The XRF analysis shows the presence xylene breaks the molecular interactions
of metals in the samples and the SEM of the nonpolar structure of HDPE.
provides information about the samples’ FTIR spectra (Figures 1 and 2) shows that
morphology. all samples present a strong absorption band
TGA was realized in a TA Instruments, closer to 1700 cm1 (stretching vibration of
SDT 2960 Simultaneous DTA-TGA model, C-O groups) that indicates carbonyl pres-
at 20 C/min, in inert (N2) and oxidant ence (C¼O),[14] which represents the esters
(synthetic air) atmospheres. FTIR analysis of biopolymers and the start of the oxidation
occurred in FT-IR System Spectrum GX/ for OXI sample. The OXI sample shows
Perkin Elmer. The SEM was made in a Jeol an absorption band referent to HDPE in
1200 with EDS (Energy Dispersive X-Ray 2919 cm1 (CH2 asymmetric stretch bonds),
Detector (EDX)) and the XRF, on an X-Ray 1452 cm1 (crystalline phase of CH2 bend),
Fluorescence spectrophotometer EDX 720/ 874 cm1 (amorphous phase of CH2 rock)
800HS Shimadzu. The analysis of biode- and 720 cm1 (crystalline phase of CH2
gradability was performed according to rock).[15]
NBR14283-1999, which specifies the proce- Biodegradable samples present an ab-
dures for the use of Bartha Respirometer. sorption band at 2960 c, representing the
Solubility tests were developed in presence asymmetric stretching vibration of CH2 and
of chloroform, xylene, toluene, hexane and an absorption band at 1711 cm1, repre-
water in room temperature and under senting the stretching vibration of C-O
heating of 100 C. bonds; BG6, BW6.1 and BW6.20 present
Seven commercial plastic bags were an absorption band at 1268 cm1, repre-
selected to this study (Table1). Six samples senting a symmetric stretching vibration of
were provided by a trade representative C-O bonds for alcohols; an absorption band
and they have the guarantee of biopolymer at 1100 cm1, representing the bending
origin; and one was collected in a market vibration at the surface of the adjacent
with a registration of conventional polymer hydrogen atoms on the phenyl ring bonds
with additives. and an absorption band at 726 cm1,
representing the bending vibration absorp-
tion of CH-plane of the benzene ring
Results bonds.[16] Data from literature indicates
that PCL/PLA spectral information shows
Biopolymer samples were soluble in chlo- absorption bands at 2920 cm1 and
roform at room temperature, but B100L 2852 cm1, representing the stretching
Table 1.
Discrimination of the samples used in the analysis.
Name Type Origin Function Color Fill
BW10 White 10 kg
BG10 Green
BG6 Green 6 kg
BW6.1 Biopolymer Trade representative Market bag White
BW6.2 White 6 kg
B100L Garbage bag Brown 100 L
OXI Oxo-degradable Supermarket Market bag White 6 kg
Table 2.
XRF for % of metals for each sample.
% BW10 BG10 BG6 BW6.1 BW6.2 B100L OXI
Calcium (Ca) 67.1 12.8 19.4 2.0 18.2 28.1 34.6
Titanium (Ti) 32.2 86.1 80.1 94.1 80.4 25.3 63.7
Copper (Cu) 0.12 0.51 0.14 0.18 0.17 0.15 0.04
Iron (Fe) 0.21 0.33 0.24 0.49 1.18 44.7 –
Sulfur (S) – – – 2.7 – – 0.5
Potassium (K) – – – – – – 0.6
Zinc (Zn) – – – – – – 0.4
Figure 4.
TGA curves of samples in oxidant (air) atmosphere.
(a) OXI, (b) BW10, (c) BG10, (d), B100L, (e) BG6, (f) BW6.1, Figure 6.
(g) BW6.2. DTG of samples in inert (N2) atmosphere.
for BW10 (Figures 6 and 7). For the other starts its degradation at 550 C and ends it
bio samples, DTG showed Td of approxi- at 800 C,[22] so the DTG (Figure 7) in an
mately 145 C (Figure 7), which may be oxidant atmosphere show peaks between
related to the melting transition of PBAT/ 483 C and 590 C.[23]
PLA with the presence of Td for PLA and FTIR and TG analysis assumed that
PBAT at both atmospheres. biodegradable samples were composed by
PHB was discarded because the results a mixture of PLA and PBAT. Considering
of thermal analysis did not show a Td close that TG and DTG curves in oxidized and
to the one expected in literature. Besides, inert atmospheres allows the study of the
this material is originated by an expensive influence of the environment in the degra-
fermentation process and it is designated to dation process, for BW10 (Figure 6), the
products with a higher added value.[21] PCL thermal curves showed that an oxidant
was also discarded because, according to environment did not present a great
literature, it should show a Ti of approxi- influence in the degradation process, which
mately 223 C and this value is not present means that the similar process may occur in
in the thermal analysis conducted. an aerobic or an anaerobic environment.
DTG in an oxidative atmosphere showed The XRF analysis (Table 2) showed a
the presence of calcium carbonate (CaCO3) higher presence of calcium and titanium in
by characteristically decomposition stages BW10 and the inverse for the other bio
and a Td of approximately 583 C (Figure 8), samples. It is known that calcium is used
confirming the presence observed on XRF like a fill and that titanium may also be used
(Table 2). According to literature, CaCO3 as a fill or as a degradant agent.[4]
The proportion of calcium and titanium
showed that the higher concentration of
calcium is not important for the degrada-
tion thermal analysis, but when the con-
centration of titanium is higher than
calcium the degradation presents better
results in oxidative atmosphere. SEM/EDS
showed a granular surface for samples
BW10 (10 kg of load) (Figure 9a) and
BG10 (Figure 9b) and for other samples
(6 kg of load) the surface is smoothed
(Figure 9c–g). EDS information was obtained
Figure 7. for samples of BW10 (Figure 9a), BG10
DTG curves of samples in oxidant (air) atmosphere. (Figure 9b) and OXI (Figure 9g), but it was
not possible to do it for other samples because
the films burned during analysis.
BW10 is a plastic bag composed by a
mixture of TPS, PLA and PBAT, added
with CaCO3 in a higher concentration than
TiO2, which promotes similar degradation
in both atmospheres. The bio samples
(BG10, BG6, BG6.1, BG6.2 and B100L)
composed by a mixture of PLA and PBAT
showed a higher concentration of TiO2
than carbonate and presented a preference
for an oxidative atmosphere, having a
Figure 8. similar behavior to the oxo-degradable
TG/DTG curves for BW10 sample in N2 an air sample. The composition of plastic bags
atmosphere. was not informed by manufactures and this
Figure 9.
SEM/EDS of samples (a) BW10, (b) BG10, (c) Bw6, (d) Bg6.1, (e) Bg6.2, (f) B100L, (g) OXI.
Figure 10.
Curve of quantify of CO2 mass produced due to biodegradation process in Bartha Respirometer. (a) BW10,
(b) BG10, (c) OXI.
presence of oxygen and in a wet environ- color, resistance and a pro-degrading action,
ment, the OXI sample presents better however, this last function depends on the
degradability than the others samples. presence of oxygen.
The samples used in this study were Biopolymers are present as a solution
composed only by biodegradable polymers, for substituting conventional polymers,
according to the representant, and did not because they present a better and a faster
degraded as expected. Actually, the samples degradation when discarded in the ideal
failed in the biodegradation test, according conditions. In Brazil, there are no compost-
to ASTM- D883-99, NBR14283-1999 and able plants to meet the biodegradable
ASTM D5209-9. The higher concentration disposal; most of the residuals are for-
of calcium and the presence of TPS indicated warded to landfills with no degradable
that both components improve the degrada- waste. The lack of standardization of the
tion/biodegradation process and the pres- composition of plastics bangs, associated
ence of titanium retards it. TiO2 is an with specific landfill features indicate the
additive with several functions and in importance of studies for a best composi-
general it is used in polymers to conferee tion of biopolymers and additives to
Figure 11.
Curve of quantification of CO2 mass produced due to the biodegradation process in Sturm Respirometer.
(a) BW10, (b) BG10, (c) OXI.
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