energies

Article
Challenges in Sustainable Degradability of Bio-Based and
Oxo-Degradable Packaging Materials during Anaerobic
Thermophilic Treatment
Magdalena Zaborowska 1, * , Katarzyna Bernat 1 , Bartosz Pszczółkowski 2 , Irena Wojnowska-Baryła 1
and Dorota Kulikowska 1

1 Department of Environmental Biotechnology, Faculty of Geoengineering,

University of Warmia and Mazury in Olsztyn, 10-719 Olsztyn, Poland; [email protected] (K.B.);
[email protected] (I.W.-B.); [email protected] (D.K.)
2 Department of Materials and Machines Technology, University of Warmia and Mazury in Olsztyn,
ul. Oczapowskiego 11, 10-719 Olsztyn, Poland; [email protected]
* Correspondence: [email protected]; Tel.: +48-89-523-4118; Fax: +48-89-523-4131

Abstract: Although the manufacturers labelled commercially available bio-based products as biodegrad-
able, there are discrepancies concerning the time frame for their sustainable biodegradation and
methane production. Starch-based, polylactic acid-based and oxo-degradable foils were anaerobically
treated in thermophilic condition (55 ◦ C, 100 days). The effect of alkaline pretreatment on foils



degradation was also investigated. To examine changes in their mechanical and physical properties,


static tensile tests and microscopic analyses, FTIR and surface roughness analyses were conducted.
Citation: Zaborowska, M.; Bernat, K.; Despite the thermophilic condition, and the longer retention time compared to that needed for
Pszczółkowski, B.; Wojnowska-Baryła, biowaste, a small amount of methane was produced with bio-based foils, even after pretreatment
I.; Kulikowska, D. Challenges in (ca. 30 vs. 50 L/kg VS) and foils only lost functional and mechanical properties. The pieces of
Sustainable Degradability of bio-based materials had only disintegrated, which means that digestate may become contaminated
Bio-Based and Oxo-Degradable
with fragments of these materials. Thus, providing guidelines for bio-based foil treatment remains a
Packaging Materials during
challenge in waste management.
Anaerobic Thermophilic Treatment.
Energies 2021, 14, 4775. https://
Keywords: biopolymers; starch- and polylactic acid-based material; methane production; surface
doi.org/10.3390/en14164775
roughness; tensile strength; FTIR and microscopic analyses
Academic Editor: Gabriele Di
Giacomo

Received: 1 July 2021 1. Introduction

Accepted: 30 July 2021 Bio-based products are defined as entirely or partially biological in origin. Among
Published: 5 August 2021 the bio-based products, biodegradable polymers (biopolymers) play an important role.
Biopolymers can be degraded by microorganisms into water and biomass, and depending
Publisher’s Note: MDPI stays neutral on whether oxygen is present, into carbon dioxide under aerobic conditions, or into carbon
with regard to jurisdictional claims in dioxide and methane under anaerobic conditions. In recent years, the share of biopolymers
published maps and institutional affil- on the market has been increasing and, in 2019, 1.174 million tons were produced at a
iations. global level. Further increases in the share of these plastics on the market are expected (i.e.,
1.334 million tons by 2024) [1,2].
One of the most known biopolymers is polylactide (PLA), which is produced by the
polymerization of lactic acid via the fermentation of dextrose derived from carbohydrate-
Copyright: © 2021 by the authors. rich crops, such as potatoes or corn. PLA is widely used because of its properties, including
Licensee MDPI, Basel, Switzerland. its biodegradability, biocompatibility, high elastic modulus, transparency and mechanical
This article is an open access article strength [3]. The other commonly used natural polymer (meaning that it is produced
distributed under the terms and directly in nature) is starch, which is, more specifically, a reserve polysaccharide composed
conditions of the Creative Commons of amylopectin (75−80%) and amylose (20−25%). Starch is used due to its abundance, inex-
Attribution (CC BY) license (https://
pensiveness, and biodegradability. It is known that, on the market, apart from biopolymers,
creativecommons.org/licenses/by/
oxo-degradable polymers are still used in some countries [4]. They contain pro-degradants
4.0/).

Energies 2021, 14, 4775. https://doi.org/10.3390/en14164775 https://www.mdpi.com/journal/energies

Energies 2021, 14, 4775 2 of 19

(e.g., d2w® or TDPA (totally degradable plastic additives)), usually produced from cobalt,
manganese, and iron compounds, which should ensure the polymer decomposition. Some
authors indicate that oxo-degradable polymers may be partially biodegradable, e.g., with
mineralization level of 12.4% after three months of incubation with compost [5].
Among the bio-based and oxo-degradable products present on the market, the most
popular are materials used for food packaging or waste bags for biowaste collection.
Because they are labelled as biodegradable, these products should be separately collected,
together with biowaste. Thus, most of the waste from these products is eventually gathered
and processed, aerobically or anaerobically, in mechanical–biological treatment plants (MBT
installations), or via a combination of the two methods. Because the share of biodegradable
polymers in the stream of selectively collected biowaste will likely continue to increase, it
is important to better understand the mechanisms and characteristics of their degradation.
Most studies have focused on the biodegradation of biopolymers under environmental
conditions, i.e., in soil, compost, and aquatic environments [6]. In aerobic conditions,
the characteristics of the process depend on the types of polymers involved (i.e., their
molecular weight, crystallinity or type of functional groups) and environmental factors (i.e.,
temperature, moisture, pH, and presence of oxygen) [7,8]. However, knowledge concerning
the possibility of polymer degradation under anaerobic conditions is limited, especially
in the context of commonly used methods for the treatment of biowaste. Therefore, it
is necessary to determine the conditions that facilitate biodegradation of bio-based and
oxo-degradable products and the characteristics of this process. Anaerobic processes seem
to be especially profitable because they produce methane, which can be used for energy
generation. However, because of amount of time needed for methane production from
bio-based products [9], pretreatment is needed. The use of pretreatment may increase the
surface area of the material, resulting in more rapid degradation and improved methane
production [10]. For example, Yu et al. [11] reported over 70% abiotic degradation of PHB
at 70 ◦ C in 4 M sodium hydroxide after 4 h of treatment. However, the treatment of PHB
in acidic solutions of sulfuric acid (0.05–2 M) at 70 ◦ C for up to 14 h did not result in
abiotic degradation. Myung et al. [12] observed the near complete abiotic degradation of
poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) at 60 ◦ C in 0.1 M sodium hydroxide
after 18 h of treatment.
In conclusion, despite many commercial products on the market being labeled as
biodegradable, their detailed compositions are not provided by manufacturers. The con-
tent of the polymer and various types of additives in the products can differ, but most
likely, the composition affects the biodegradability of polymers and the time frame for
their biodegradation, especially in the context of their end-of-life considerations in waste
management. Thus, in the present study, degradability and methane production (MP) from
commercially available bio-based foils based on starch (FS), polylactic acid (PLA), and ad-
ditionally oxo-degradable product (OXO), was analyzed. Moreover, alkaline pretreatment
was used to check the acceleration of the process. Microscopic and FTIR analyses, and
determination of the functional properties of the surfaces and the mechanical properties of
the materials (static tensile tests) were also performed. Determination of the mechanical
properties of material, as another indicator of its degradation, is not a common practice.

2. Materials and Methods

2.1. Bio-Based and Oxo-Degradable Materials Used in the Experiment
In the experiment, commonly available waste bags made of bio-based materials and
oxo-degradable material were used. As bio-based materials, BioBag waste bags made from
Mater-Bi® material based on starch (FS) and bags made from polylactic acid (PLA) were
used. The oxo-degradable waste bag (OXO) was made from petroleum-based polyethylene
containing d2w pro-degradant additive. The characteristics of the materials are as follows:
• PLA (the VS content of 99.3 % DM, 71.5 g COD/kg DM, 454.9 mg Ntot /kg DM);
• FS (the VS content of 99.9 % DM, 63.9 g COD/kg DM, 408.6 mg Ntot /kg DM);
Energies 2021, 14, 4775 3 of 19

• OXO (the VS content of 93.1 % DM, 3766.8 mg Ntot /kg DM (COD was not possible
to determine)).
The products were obtained from the commercial public market; thus, they may have
contained other additives, improving their functional properties but, unfortunately, the
manufacturer did not report their detailed composition. The waste bags were shredded to
a particle size of 10 × 10 mm.
Two sets of experiments were carried out. In the first, all materials (PLA, FS, OXO)
were used without pretreatment. In the second set, PLA, FS and OXO were pretreated
with 0.1 M potassium hydroxide (KOH) for 2 h; pretreatment was performed at ambient
temperature (PLAKOH , FSKOH , OXOKOH ). After 2 h, the mixture was neutralized with
hydrochloric acid. Solubilized PLA (PLAsolubilized ) and FS (FSsolubilized ) were used as
control samples. Each material was solubilized with the use of 1 M KOH for 24 h. The
OXO material did not solubilize under these conditions.

2.2. Measurement of Methane Production (MP) under Thermophilic Conditions

The anaerobic degradation test of bio-based and oxo-degradable products was carried
out in thermophilic conditions (55 ◦ C). The experiment was carried out in a methane
potential analysis device (Automatic Methane Potential Test System, AMPTS II, Bioprocess
Control, Sweden AB) for 100 days. The device consisted of reactors with a volume of
630 mL. The reactors were mixed at a speed of 80 rpm for 1 min every hour. To each
reactor, 200 mL of inoculum and the appropriate amount of material was added to ensure a
starting organic load of 4 kg VS/m3 . Anaerobic conditions were achieved by flushing each
reactor with pure nitrogen for 2 min. The inoculum was obtained from a closed chamber
for the mesophilic anaerobic digestion of sewage sludge. Thermophilic preincubation of
the inoculum was carried out at 55 ◦ C for 14 days. The dry mass (DM) content of the
inoculum was approximately 1.7%, whereas VS constituted 69.5% of DM.
The anaerobic degradation test was based on determining the volume of methane
produced online. The measurement of MP with each material and inoculum, and with
inoculum alone was performed in triplicate. In order to not disturb the MP in the AMPTS II,
additional glass bottles were prepared for sampling for microscopic analysis, and roughness
and static tensile tests. These bottles had the same volume as the reactors used in the
AMPTS II and were dosed with the same amount of inoculum and material, and placed in
a thermostatic incubator at 55 ◦ C. When the fragments of bio-based and oxo-degradable
materials were collected for analysis, they were cleaned with distilled water.
Based on the anaerobic degradation test in the methane potential system, the biodegra-
dation degree (BD) was assumed. The BD of the bio-based materials (PLA, FS, PLAKOH and
FSKOH ) during anaerobic treatment at 55 ◦ C was calculated as the ratio of the cumulative
MP from the material (after pretreatment (treated) or without pretreatment (untreated))
to the cumulative MP from the material after its solubilization. The cumulative MP from
the solubilized material was assumed to be the maximal MP from this material under the
experimental conditions. For the OXO material, which did not solubilize, the BD was
not determinable.
Methane production (MP) followed pseudo first-order kinetics, and can be described
with this equation:
Ct,CH4 = CCH4 · (1 − ekCH4 t)+ C0,CH4 , (1)
where Ct;CH4 (L/kg VS) is the cumulative MP at time t (days) of anaerobic measurement;
CCH4 (L/kg VS) is the maximal MP; C0,CH4 (L/kg VS) is the initial MP; kCH4 (d−1 ) is the
kinetic coefficient of MP.
The rate of MP is the product of CCH4 and kCH4 .
The values of CCH4 , C0,CH4 and kCH4 were obtained by nonlinear regression analysis
with Statistica software, version 13.0 (StatSoft, Tulsa, OK, USA).
Energies 2021, 14, 4775 4 of 19

2.3. Microscopic and FTIR Analysis

During anaerobic degradation tests, pieces of FS, PLA, OXO, PLAKOH , FSKOH , and
OXOKOH were removed from the inoculum and cleaned with distilled water for the micro-
scopic analysis, and the roughness and static tensile tests.
The changes on the surface of the bio-based and oxo-degradable materials were
analyzed using a Nikon eclipse50i (Nikon, Tokyo, Japan) polarizing microscope at a
magnification of 10×. Pictures were taken at 0, 20, 45, 59 and 100 days.
The FTIR spectra (with three replicates for each foil material) were obtained using a
Perkin Elmer Spectrum Two (with diamond ATR) (Perkin Elmer, Waltham, MA, USA) brand
device having a resolution of 4 cm−1 within the wavenumber range of 4000–400 cm−1 at
room temperature.

2.4. Functional Properties of the Surface

The geometric structure of the surface and the functional properties of the fragments
of foils (five replications) were performed with the profile method (PN-ISO 3274) using
a Mitutoyo Surftest SJ-210 profilometer (Mitutoyo, Kawasaki, Japan) with a diamond
measuring tip with a point angle of 60◦ and a stylus radius of 2 µm. The measured
length for each material consisted of five elementary sections that were 0.8 mm long.
The changes in amplitude (arithmetical mean roughness value (Ra), mean square surface
profile deviation (Rq)) were determined. The Abbott–Firestone curves [13] were used to
determine the reduced peak height without bearing properties (Rpk); the roughness core
height (roughness core profile), characterizing the surface bearing properties (Rk); the
reduced valleys depth, characterizing the ability of the surface to hold liquids (Rvk); total
height of the roughness profile (Rt) and the percentage of the peaks and valleys (Mr1, Mr2,
respectively). A detailed description is given in [14].

2.5. Static Tensile Tests

Static tensile tests (tensile strength at break and elongation at break) were performed
according to ISO standard (ISO 527-2:2012, ISO 527-3:2019) with the use of a TA.HD.Plus
(Stable Microsystems, Surrey, UK). Five replicate samples of foils were used for the mea-
surements until they were too fragile for analysis, and it was impossible to place them in
the tensile test device. The samples were subjected to a tensile force at a constant speed
until the moment of fracture.

2.6. Analytical Methods

The volatile substance (VS) content of the FS, PLA and OXO materials was determined
as loss after ignition at 550 ◦ C. The chemical oxygen demand (COD) of these materials
and the content of nitrogen (Kiejdahl nitrogen) were also determined. All physicochemical
analyses were performed according to Greenberg et al. [15]. Flash 2000 Organic Elemental
Analyzer (Thermo Scientific, Milan, Italy) was used to determine elemental composition of
bio-based materials according to the manufacturer’s protocol.

3. Results and Discussion

3.1. Methane Production during Anaerobic Test
Biodegradation anaerobic of pieces of waste bags made of PLA, FS, OXO, and also
the materials after pretreatment (PLAKOH , FS KOH , and OXOKOH ) were carried out under
thermophilic conditions at 55 ◦ C. The MP analysis tool allowed measurement of the volume
of methane (in mL) produced online. Two MP profiles are considered during the analyses
of each material: the first profile corresponds to the inoculum alone, and the second, to
both the inoculum and the material. By subtracting the values of the first profile from
the second, the profile of the methane volume for the material alone is obtained. In the
present study, the VS content of the materials was considered to reflect the organic matter
content, and the MP was shown as L/kg VS (Figure 1). To improve the readability of the
figure, 60 days of measurements are shown, although the time of measurements was ca.
Energies 2021, 14, 4775 5 of 19

100 days. The OXO material did not degrade; thus, no MP was observed, and the profiles
are not provided.

Figure 1. Methane production profiles during an anaerobic degradation test at 55 ◦ C of bio-based materials made of PLA
and FS without pretreatment (a,b), of these materials with pretreatment (c,d), and solubilized materials (e,f); to improve the
readability of the figure, 60 days of measurements are shown, although the time of measurements was ca. 100 days.

Regarding bio-based materials made of PLA and FS without pretreatment, lag phases
in MP were observed. With FS, the lag phase was shorter, lasting 6 days, whereas with
PLA, it lasted 7 days. After the lag phase, MP increased until day 15 or 16 of measurements.
Then, the methane volumes remained the same until the end of the anaerobic test, which
lasted almost 100 days, and the final methane volumes for PLA and FS were similar, 34.5
and 32.7 L/kg VS, respectively.
Energies 2021, 14, 4775 6 of 19

After pretreatment, the lag phases shortened to 4 days for both PLAKOH and FSKOH ,
and after this time, intensive MP took place. After the lag phase, during next 6 days of
measurement, PLAKOH produced 47.5 L/kg VS, whereas FSKOH produced almost 25%
more, 58.6 L/kg VS.
When solubilized materials were investigated in anaerobic degradation tests, it was
found that MP started from the beginning of the measurements. After 15 and 12 days of
the measurements with PLAsolubilized and FSsolubilized , respectively, MP reached maximum.
Despite the fact that PLA needed a longer time to obtain maximum MP, the final value
was 1.3 times higher than MP with FS (162 L/kg VS for PLAsolubilized vs. 125 L/kg VS for
FS solubilized ).
Cumulative MP after 100 days of anaerobic treatment of PLA and FS, without pre-
treatment, with pretreatment, and the solubilized materials, is shown in Figure 2a. To
summarize, cumulative MP was similar with both materials without pretreatment. After
pretreatment, cumulative MP with PLAKOH and FSKOH increased almost 40% and 80%,
respectively; with the solubilized materials, it was highest. However, the values were much
lower than with pure PLA and pure starch materials.

Figure 2. Cumulative methane production after 100 days of anaerobic degradation of PLA and FS (a), the rate of methane
production (b), and the biodegradation degree (BD) (c).

Methane production proceeded with first-order kinetics, and the model fit the experi-
mental data well (R2 = 0.98–0.99). The kinetic models and the initial rates of MP are shown
in Figure 1.
The rates of MP, summarized in Figure 2b, corresponded with the cumulative MP with
untreated and treated materials. However, the rates of MP with both solubilized materials
were similar, despite the difference in cumulative MP.
It was assumed that the solubilized materials (PLAsolubilized and FSsolubilized , i.e.,
control samples) produced the maximal methane volume, and this equaled 100% of the
biodegradation degree (BD) of these materials. For PLA without pretreatment and FS
without pretreatment, BD was higher for FS, but for both of the materials, it did not exceed
26% in comparison with solubilize materials. The BD of PLAKOH FSKOH increased to 30
and 47.5%, respectively (Figure 2c).
Energies 2021, 14, 4775 7 of 19

It should be emphasized that, during the long-term anaerobic biodegradation test, the
pieces of the materials were still visible in the inoculum, and they did not disintegrate, as
shown by the microscopic analyses.
The elemental compositions of the bio-based products, PLA and FS, were determined
(Table 1).

Table 1. Elemental composition, empirical formula, and theoretical methane production (TMP) of foil materials (PLA, FS)
and of pure polymers (pure PLA, pure FS).

Characteristics Pure PLA PLA Pure FS FS

Empirical formula C3 H4 O2 C4.4 H6.31 O2 C6 H10 O5 C9.8 H14.7 O5
Elemental composition
Carbon, % TS 50.00 57.56 44.44 55.36
Hydrogen, % TS 5.56 6.88 6.17 6.90
Oxygen, % TS 44.44 34.86 49.38 37.64
Methane production
* TMP, L/kg 467 610 413 577
** MP, L/kg – 162 – 125
* TMP calculated using the Buswell equation [16]; ** cumulative methane production (MP) after 100 days of anaerobic thermophilic
treatment of solubilized PLA and FS.

PLA contained more carbon and less oxygen than S. The hydrogen content of both
foils was about 6.9%. However, it must be emphasized that both foils (PLA, FS) contained
more C and H than pure PLA and pure FS, with lower content of O.
The FS foil material is described by the manufacturer as consisting mainly (as much as
85% or more) of modified thermoplastic starch that is biodegradable and compostable [17].
On the basis of the elementary composition of the foil materials and pure polymers (pure
PLA, pure FS), the theoretical amounts of methane (TMP) and carbon dioxide that could be
obtained, assuming complete conversion of organics into biogas, were calculated using the
Buswell equation [16]:
     
b c a b c a b c
Ca Hb Oc + a − − H2 O → − + CO2 + + − CH4 (2)
4 2 2 8 4 2 8 4

The TMP values of pure PLA and pure FS were approximately 1.3–1.4-times lower
than those of the PLA and FS foils, due to the lower carbon and hydrogen contents of the
pure materials (Table 1). As for the cumulative MP during anaerobic digestion at 55◦ C, PLA
and FS produced more than two-times less methane than PLAsolubilized and FSsolubilized .
However, even solubilized materials produced methane in amounts constituted only 27%
and 22%, respectively, of the TMP values. The small amount of methane produced by
all the bio-based materials is connected with the fact that, until 100 days of anaerobic
degradation had passed, pieces of the foils were still visible in the inoculum, and these
fragments only disintegrated when they were touched.
The results concerning anaerobic treatment of starch-based material are scarce. For
example, Mohee et al. [18] found that the cumulative methane production from starch-
based material was of 245 mL over 32 days of batch digestion assays. The value was much
higher than that obtained in the present study; however, the authors did not provide the
initial doses of the material. Therefore, it is not known what the methane production was
per 1 g VS, and the efficiency of the process cannot be estimated.
Studies with PLA are more numerous, however, most of them are carried out with the
used of pure polymer, not with commercially available foil materials. Itävaara et al. [19]
found that at temperatures of 37 ◦ C during 40 days of measurements PLA degradation was
not higher than 5%. They reported 60% of PLA degradation after 100 days of an anaerobic
test without providing more specific information. Under thermophilic conditions, about
60% of PLA was also degraded, but after 40 days. Contrarily, the results of Yagi et al. [20]
showed that PLA biodegradability was 80–91% in aquatic conditions at a thermophilic
Energies 2021, 14, 4775 8 of 19

temperature. In another study, Yagi et al. [21] found approximately 60% biodegradability
of PLA powder of 90% in 60 days under thermophilic conditions. However, these studies
focused on the biodegradation degree but without determination of the efficiency of
methane production. The recovery of energy from municipal waste one of the main key
points of the strategy of circular economy. Thus, it is important to determine the biogas
potential of packaging materials (foils) considered to be biodegradable. This was done in
the present study.

3.2. Changes in the Structure of Tested Materials—Microscopic Analysis

At the beginning, the foil pieces of the investigated materials looked like typical foil
waste bag materials, and all of them were green in color and smooth.
Microscopic images of the structure of untreated and treated foils were present in
Figure 3. Regarding the structure of FS, the changes were visible from the 28th day of
degradation, whereas changes in the structure of PLA were visible from about the 59th
day. When the changes became apparent, there were individual cracks and fissures in the
structure. After this time, the cracks and fissures had become deeper and more numerous on
the surface. Unfortunately, both of the bio-based materials did not disintegrate completely,
and they were still visible until almost 100 days of anaerobic treatment. The use of the
pretreatment step did not facilitate the process of disintegration of the bio-based foils. The
visible changes, in the form of cracks and fissures, appeared on the surface of foils around
the same time as in the variant without pretreatment. However, the pretreatment step
caused the foil pieces to become severely weakened and fragile, so that they crumbled
when touched after a shorter time of degradation.
As mentioned, the OXO foil did not produce methane, and microscopic analyses did
not show any structural changes even after the pretreatment step.

3.3. Changes in the Mechanical Properties of the Materials

During the anaerobic degradation test, the mechanical properties of the foils before
and after the pretreatment were investigated. The results of tensile strength are presented in
Figure 4a,b. Regarding the untreated OXO material, the tensile strength decreased by about
17.5 ± 6.8% in the first 10 days of the experiment. Then, until the end of the test, the tensile
strength remained at a similar level. The initial decrease could result from the presence
of the oxo-degradant, which may weaken the mechanical properties of polyethylene (PE)
under thermophilic conditions [22,23].
Regarding the bio-based products without pretreatment, a decrease in tensile strength
was observed, which indicated that degradation was progressing (Figure 4). It was possible
to measure the tensile strength of FS until to the 39th day of the anaerobic degradation
test, at which point the tensile strength had decreased by almost three fold. After this
time, the foil was too brittle to be subjected to the strength test and it was not possible to
place particles of FS in the measuring device. During the first 10 days, the tensile strength
decreased sharply, from 16.6 ± 0.8 MPa in the raw material, to 11.1 ± 0.7 MPa. After
this time, the tensile strength continued to decrease steadily, and after 39 days, it reached
5.9 ± 0.9 MPa (Figure 4a).
Tensile strength measurements of PLA were possible until the 59th day of the test,
which means that, in this regard, the material was more resistant than FS.
Energies 2021, 14, x FOR PEER REVIEW 9 of 20
Energies 2021, 14, 4775 9 of 19

Time (d) PLA PLAKOH FS FS KOH OXO OXOKOH

20

45

59

100

Figure 3. Microscopic images of the structure of untreated and treated foil materials during anaerobic thermophilic degradation test.
Energies 2021, 14, 4775 10 of 19

Figure 4. Changes in the mechanical properties (tensile strength and elongation at break ε) during an anaerobic degradation
test of untreated foils (a,b) and foils after pretreatment with KOH (c,d).

Up to day 14 of the experiment, the tensile strength of PLA increased by about 9%

because the material stiffened. Vasile et al. [24] carried out burial soil degradation of pure
PLA and found that, after an initial decrease in tensile strength by about 14% on day 50,
the material stiffened slightly, corresponding to a tensile strength increase after 100 days.
After 150 days, the tensile strength decreased again. Stiffening of PLA may be caused by
the water diffusing into the amorphous region of the material and random scission of ester
bonds. This causes an increase in the degree of crystallinity during the degradation process.
Next, after the degradation of the amorphous regions, degradation proceeds towards the
center of the crystalline parts [25,26].
In the present study, the tensile strength of the PLA continuously decreased from day
14 to day 52 of the test, reaching 11.3 ± 1.0 MPa. On the last day, the PLA material was still
collectible for the test, and the tensile strength was 3.6 ± 2.0 MPa, which was almost six
times lower than in the raw/starting material (Figure 4a).
Rajesh et al. [27] carried out the soil burial degradation of pure PLA for 90 days at
room temperature. Before starting degradation, the tensile strength of the material was
50 MPa and, during their study, it decreased by 26.5% (to ca. 38 MPa). Compared to the
present study, the reduction in tensile strength was much smaller, but the tensile strength
values were much higher. It should be emphasized that those authors conducted their
degradation tests under aerobic conditions at room temperature, and they used pure PLA,
Energies 2021, 14, 4775 11 of 19

which has greater tensile strength than the material used in the study presented here. The
decrease in the tensile strength of bio-based products during degradation tests may be
caused by the diffusion of water into the polymer matrix, causing hydrolysis to begin
faster [28].
Then, as a result of breaking the secondary bonds (hydrogen, van der Waals bonds),
the polymer is weakened, and the long polymer chains are converted to chains of low
molecular weight. Then, the covalent bonds between the monomers are broken, which
continues until the polymer is completely degraded [29].
The elongation at break (ε) of PLA, FS and OXO was also determined (Figure 4b,d).
The value of ε for OXO material slightly decreased during the first 10 days of the degrada-
tion test, but over the next few days, only the small changes were noted. However, it should
be emphasized that the initial ε of OXO was the highest of all the tested materials (375%),
in contrast to its tensile strength, which was similar to that of the other foil materials.
Generally, the ε value of FS and PLA decreased as anaerobic degradation progressed.
Despite the fact that the tensile strengths of both materials were similar, the elongation
at the break of PLA was almost two-times higher than that of FS (ca. 220% and ca. 120%,
respectively). However, in the case of PLA foil, a rapid initial decrease in ε (to ca. 85%)
corresponded to the initial increase in tensile strength (from ca. 21 to ca. 23 MPa). The
material may have stiffened due to an increase in its degree of crystallinity, which caused
its tensile strength to increase. Then, at ca. 15 days, its elongation at break increased to
135%, which may have been caused by the breakdown of the secondary bonds between the
polymer chains. From day 14 to day 45, the ε value decreased, reaching ca. 7%, which was
only 3.2% of the initial value. The ε value then remained the same until the 59th day of
the test, when the last measurement of this characteristic was possible. Regarding FS, its ε
value increased by about 6% (from ca. 122%) during the first 10 days of measurement. This
might have been caused by the polymer absorbing water. Then, at day 39, when the last
measurement was possible, ε had decreased to ca. 10 ± 2% (Figure 4b,d).
The tensile strength and ε of KOH-pretreated OXO were virtually the same as those
of OXO that had not been pretreated. Initially, the tensile strength slowly decreased, and
after the 14th it was 22 ± 6% lower than the initial value. Then, the tensile strength
and ε remained the same until the end of the degradation test. However, it should be
emphasized that the KOH-pretreatment of OXO increased the standard deviation of the ε
values (Figure 4c,d).
In contrast, pretreatment weakened the mechanical properties of both bio-based
materials. Moreover, the time during which it was possible to determine the mechanical
properties of these two foils was shorter with pretreatment than without pretreatment (for
PLAKOH , reduced from 52 to 28 days; for FSKOH , from 39 to 35 days).
After 7 days of anaerobic degradation of PLAKOH , the tensile strength decreased by
about 11 ± 4% in comparison to the raw material (ca. 21 MPa). No temporary stiffness
was observed, unlike the PLA, which was not pretreated. This lack of stiffness was also
confirmed by the fact that, during this time, elongation at break decreased rapidly to 45%,
which was almost two-times lower than the value obtained during the first days with
the untreated PLA. Until 21 days of the test, the tensile strength remained at a similar
level, while ε decreased slightly. Then, at 28 days, the tensile strength and ε decreased to
ca. 8 MPa and 5%, respectively. With regard to both FS and FSKOH , the tensile strength
decreased sharply to ca. 10 MPa within the first 10 days of degradation.
In general, the decrease in elongation at the break of both the pretreated bio-based
products and those without pretreatment was caused by an increase in the stiffness and a
decrease in the flexibility of those materials. Similarly, Vasile et al. [24] reported that the
tensile strength and elongation at break of pure PLA materials and PLA biocomposites
decreased during soil burial biodegradation. The authors stated that, as the time of
degradation progressed, the stiffness of the investigated materials increased.
Energies 2021, 14, 4775 12 of 19

3.4. Changes in the Surface Roughness of the Foils

During anaerobic degradation, the surface roughness of the foils decreased. Measure-
ments of roughness were carried out to days 59 and 53 of degradation of the untreated and
treated foils, respectively. After this time, the foils were too brittle to be analyzed.
During the first 9 days of anaerobic degradation, the Ra, Rq and Rt values of untreated
PLA decreased, corresponding to a decrease in the roughness core (Rk). In addition, the
reduced valley depth (Rvk) also decreased. Taken together, the decreases in these values
indicated that the roughness of the PLA decreased, which may be due to the diffusion of
the inoculum into the polymer matrix and water adsorption by the polymer. From day 9 to
day 20, the Ra, Rq, Rt values increased, and on day 28, these values were similar to values
noted in the raw material. In contrast, the Rpk value decreased until day 4, and then until
day 14, it increased more than 2-times, and then remained at a similar level until the end of
the measurements (Figures 5 and 6).
Until day 45, the the Ra, Rq, Rt values for PLA decreased again by about 1.4–1.5 times
compared to the raw material, which was probably related to the secondary diffusion of
water into the material structure. This also may indicate a gradual decrease in the thickness
of the foil. The percentage of the peaks and valleys (Mr1 and Mr2) remained at a same
level until day 45, then slightly decreased.
Regarding the FS foil, the Ra, Rq and Rt values increased during the first days of the
anaerobic testing, which may indicate that the top layer of the material quickly dissolved.
The structure of the material then became more complex and non-homogeneous. The
roughness (Ra, Rq, Rt, Rk) of foil FS decreased to the 39th day of the analysis, and after this
time, it remained at a constant level. However, the total height of the profile (Rt) increased,
which may mean that larger random height peaks occurred in the structure, which are
characteristic of damage to the surface structure.
Regarding the OXO foil, the roughness indicators did not display any differences up to
day 14, and then, on day 20, all of these values except Mr1 and Mr2 increased 1.7–2.3-times.
After day 20, all roughness indicators decreased. However, on the 59th day of degradation,
the Ra, Rq, Rt, Rk, Rpk and Rvk values increased, which may have been related to the
removal of oxo-additives from the surface structure. During the degradation test, the value
of Mr1 decreased slightly, while that of Mr2 remained at a similar level (Figures 5 and 6).
Generally, after the pretreatment with KOH, the roughness of the bio-based materials
decreased. This may be due to degradation of the external layers of the foils. However,
the MR2 and MR1 values remained at a level similar to that in the untreated materials
(Figures 5 and 6).
The pretreatment caused the initial weakening of the surface structure of the PLA.
After the pretreatment with KOH, binding of PLA and KOH might have taken place, which
would have created a layer that partially blocked the pores in the structure, resulting in the
lack of change in the roughness indicators. The slight fluctuations in their values may have
resulted from the damage to the surface of the materials after pretreatment. The Ra, Rq, Rt,
Rk, Rpk and Rvk values decreased on day 53 of the anaerobic test. This may indicate that
particles were rinsed out of the material into the inoculum. Moreover, the lower Rk value
indicated a decrease in the roughness core, which could be connected with damage to the
top layer of the material. At this time, the material defragmented when it was touched and
further determination of the surface roughness was not possible. In contrast, Luo et al. [30]
found that, in compost conditions, the neat PLA did not present significant changes on the
surface after 5 days biodegradation, but after 20 days, the surface roughness increased. This
could be owned to the hydrolysis of PLA and microorganism activities. With increasing
incubation time, the cracks and voids became substantially deep and large.
Energies 2021, 14, 4775 13 of 19

Figure 5. The surface roughness indicators (arithmetical mean roughness value (Ra), mean square surface profile deviation
(Rq), the roughness core height (roughness core profile) (Rk), total height of the roughness profile (Rt)) during an anaerobic
degradation test of untreated foils (PLA, FS, OXO) (a,c,e,g) and foils after pretreatment with KOH (PLAKOH , FSKOH ,
OXOKOH ) (b,d,f,h).
Energies 2021, 14, 4775 14 of 19

Figure 6. The surface roughness indicators (the reduced peak height without bearing properties (Rpk), the reduced valleys
depth (Rvk); the percentage of the peaks and valleys (Mr1, Mr2, respectively)) during an anaerobic degradation test of
untreated foils (PLA, FS, OXO) (a,c,e,g) and foils after pretreatment with KOH (PLAKOH , FSKOH , OXOKOH ) (b,d,f,h).
Energies 2021, 14, 4775 15 of 19

After the KOH pretreatment, the roughness indicators of the FS were lower than those
of the untreated material, and they decreased with time until 14 days of the anaerobic
test had passed, indicating rapid initial degradation of S. The changes in the values of the
roughness indicators corresponded to changes in the MP profile. The lag phase of MP
lasted only 4 days and was shorter with pretreated material than with untreated foil, and
after this time methane started to be produced rapidly until day 15.
Cumulative MP was higher with treated FS than with the untreated material. Between
15 and 35 days of the test, the roughness indicators did not change much. On day 53, these
values differed from what was observed on the other days. This was connected with the
non-homogenous structure of SKOH and the presence of small, deep micropores on the
surface, which increased the roughness indicator values.
The pretreatment of OXO foil caused the initial values of its roughness indicators to be
higher than those of the untreated material. This might have been caused by rapid removal
of oxo-additives from the surface structure of OXO. It should be emphasized that the OXO
was very rough and heterogenous in its structure. The polymer was not damaged during
the anaerobic test, even after the pretreatment, and the changes in its roughness resulted
from this heterogenous structure and degradation of the oxo-additive.

3.5. Changes in the Structure of Bio-Based and Oxo-Degradable Foil Materials—FTIR Analysis
Regarding the raw PLA foil material, the FTIR analysis showed typical peaks for
pure PLA. Hydrogen-bonded (intra- and intermolecular) -OH groups corresponded to
the band at 3371 cm−1 . The asymmetric and symmetric vibrations of the -CH3 groups
were represented by the bands located at 3000–2850 cm−1 . The strong band at 1713 cm−1
indicated asymmetric stretching of carbonyl C=O groups, which may correspond to the
amorphous phase of PLA.
In contrast, if a weak band is observed at ~1720 cm−1 , it may be assigned to C=O
stretching of the crystalline phase of PLA [31]. The bands at 1271, 1104, and 1019 cm−1
corresponded to stretching vibrations of the C-O-C and -CH-O- groups. The band at
930 cm−1 combined contributions of both -CH3 rocking and deformation of the carboxylic
-OH . . . H groups [32]. The O-CH-CH3 , esters and/or C-C and rocking vibrations of -CH3
groups were noted at 874 and 727 cm−1 , respectively (Figure 7).
With the untreated PLA foil material, the intensity of all bands increased after ca.
100 days of the anaerobic thermophilic test, except the one corresponding to -OH (at
3371 cm−1 ), which indicated PLA degradation. For example, the intensity of the peak at
1713 cm−1 increased, which corresponds to a larger amount of carbonyl C=O groups, which
are terminal groups in PLA chains. This indicates that the molecular weight of the PLA
chains decreased. Although high molecular weight PLA is insoluble in water, during the
degradation process, water diffuses into the polymer matrix, causing the hydrolysis of the
ester groups of the amorphous phase. As a result, short-chain soluble carboxyl-terminated
oligomers and monomers are formed and penetrate the aqueous environment. This causes
an increase in the number of carboxyl chain ends, which was shown by the greater intensity
of the peak corresponding to this group [33,34].
On the contrary, with PLA foil pretreated with KOH, the intensity of all bands de-
creased. However, in both cases biodegradation took place, which was confirmed by the
weakness of the mechanical properties of the material and MP.
However, the time during which it was possible to determine the mechanical prop-
erties of PLAKOH was 28 days, which was almost 2 two times shorter than that during
which the properties of PLA could be determined. Pretreatment influenced the mechanical
properties more than biogas production.
Energies 2021, 14, 4775 16 of 19

Figure 7. FTIR spectra of untreated foil materials (PLA, FS, OXO) (a,c,e) and foil materials after pretreatment with KOH
(PLAKOH , FSKOH , OXOKOH ) (b,d,f) before and after 100 days of anaerobic degradation at 55 ◦ C.

Vasile et al. [24] found that, during the degradation of PLA and its composite in soil
burial conditions, degradation included the ester groups destroyed by hydrolysis.
In the present study, the intensity of the ATR-FT-IR spectra decreased due to hydrolytic
degradation. These results are consistent with those in the literature, Maharana et al. [35]
concluded that chain scission of the PLA main chain takes place where the ester bonds are
located, leading to the formation of oligomers.
Regarding the raw FS foil material, the bands at 2915 cm−1 indicated C–H stretching in
aliphatic and aromatic groups (Figure 7). The bands at 1715 and 1272 cm−1 corresponded to
C=O groups and C–O bonds found in ester linkages. The peak at 1019 cm−1 was caused by
Energies 2021, 14, 4775 17 of 19

the stretching of phenylene groups. The band at 727 cm−1 indicated four or more adjacent
methylene (–CH2 –) groups. The FTIR spectra of FS foil contained bands characteristic
of plasticized starch. The peaks between 3558–3100 cm−1 and between 1269–900 cm−1
corresponded to O–H stretching groups and to C-O stretching and hydrogen bonding
peaks, respectively. The peaks recorded at 1140 and 1103 cm−1 corresponded to C–O
stretching in the C–O–H group. At 1016 cm−1 , evidence of C–O stretching in the C–O–
C group of the starch anhydroglucose ring could be seen. After 100 days of anaerobic
degradation of untreated FS foil material, the bands in the FTIR spectrum were almost
identical to those in the spectrum of the raw material, and no new peaks were formed.
Only the intensity of the spectra increased.
Regarding the treated FS foil material, the bands in the FTIR spectrum and their
intensities were even more similar to those in the spectrum obtained from the raw material.
It should be emphasized that pretreatment weakened the mechanical properties of the
material more rapidly, and FSKOH produced 80% more methane than FS. Thus, the FTIR
spectrums that were obtained after degradation of FS and FSKOH differed.
The FTIR spectra of OXO and OXOKOH were typical of PE (Figure 7). The bands
at 2849 and 2846 cm−1 corresponded to C–H stretching asymmetric and symmetric vi-
brations, whereas the band at 1464 cm−1 was due to scissoring CH2 groups. The bands
at 720 cm−1 and 717 cm−1 were caused by CH2 rocking vibrations. A small band was
noted at 1630 cm−1 , related to a double bond (or aromatic rings), probably due to some
surface antioxidant additive. The spectra obtained from the material after 100 days of
anaerobic treatment displayed lower intensity peaks. The band at 1630 cm−1 was not
observed, which means that the antioxidant additive was washed away or assimilated by
bacteria and the spectrum was from pure PE [36]. As a result of the disappearance of the
additive, the OXO chains shortened, which slightly weakened the mechanical properties of
the material. Degradation of modified polyethylene can proceed via two mechanisms (i)
hydro-biodegradation and (ii) oxo-biodegradation, depending on the two additives, starch
or pro-oxidant, used in the synthesis polymer [37]. Starch blend polyethylene contains
starch inclusions which makes the material hydrophilic and, therefore, microbial amylase
enzymes can easily access, attack and remove this part.
Polyethylene with pro-oxidant additive can be photodegraded and chemically de-
graded, and low molecular weight products are sequentially oxidized [38,39].

4. Conclusions
Because the share of usable polymers has increased in municipal waste streams, it
is necessary to the determine the degradability of these materials, which is the current
challenge of organic recycling strategies. It was shown that untreated and treated OXO
did not degrade; thus, there was no methane production and no visible changes on the
surface or in the mechanical properties. Untreated bio-based foils began to lose mechanical
properties by day 50 of the anaerobic thermophilic degradation test; the pieces were still
visible even after 100 days, and they only disintegrated when touched. Cumulative MP
reached only 34 L/kg VS. After pretreatment, cumulative MP increased to 47.5 L/kg
VS (PLAKOH ) and 58.6 L/kg VS (FSKOH ). However, these values constituted only 8–
10% of the theoretical MP. Pretreatment of bio-based foils increased surface damage and
weakened their mechanical properties (tensile strength, elongation at break). This means
that the pieces of bio-based materials may contaminate digestate at municipal waste
treatment plant.

Author Contributions: Conceptualization, M.Z. and K.B.; methodology, M.Z., K.B., and B.P.; formal
analysis, K.B., I.W.-B., and D.K.; validation, M.Z. and B.P.; investigation, M.Z., B.P., and K.B.; resources,
M.Z., K.B., I.W.-B., and D.K.; data curation, M.Z. and K.B.; writing—original draft preparation, M.Z.,
K.B., B.P., and D.K.; writing—review and editing, M.Z., B.P., K.B., I.W.-B., and D.K.; visualization,
M.Z. and B.P.; supervision, K.B.; funding acquisition, K.B., I.W.-B., and D.K. All authors have read
and agreed to the published version of the manuscript.
Energies 2021, 14, 4775 18 of 19

Funding: We are grateful for the financial support of the Ministry of Science and Higher Education,
Poland (statutory project No. 29.610.024-110). Publication (Open Access) of this research was
financially co-supported by Minister of Science and Higher Education in the range of the program
entitled “Regional Initiative of Excellence” for the years 2019–2022, Project No. 010/RID/2018/19,
amount of funding 12,000,000 PLN.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.

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