Received: 2 June 2020 Revised: 11 September 2020 Accepted: 13 September 2020

DOI: 10.1002/app.50020

ARTICLE

Field performance on lettuce crops of poly(butylene

adipate-co-terephthalate)/polylactic acid as alternative
biodegradable composites mulching films

Alana G. de Souza | Rafaela R. Ferreira | Julio Harada | Derval S. Rosa

Centro de Engenharia, Modelagem e

Ciências Sociais Aplicadas, CECS/
Universidade Federal do ABC (UFABC),
Santo André, Brazil
Correspondence
Derval S. Rosa, Universidade Federal do
ABC, Centro de Engenharia, Modelagem
e Ciências Sociais Aplicadas, Avenida dos
Estados, 5001, Santo André, SP CEP
09210-580, Brazil.
Email: dervalrosa@yahoo.com.br
Funding information
Conselho Nacional de Desenvolvimento
Científico e Tecnológico, Grant/Award
Numbers: 305819/2017-8, 306401/2013-4;
Fundaç~ao de Amparo à Pesquisa do
Estado de S~ao Paulo, Grant/Award
Number: 2018/11277-7
Abstract
This work developed biodegradable poly(butylene adipate-co-terephthalate)/
polylactic acid (PBAT/PLA) composites with different fillers to improve their
physicochemical properties and biodegradability. The films were tested consid-
ering mechanical, morphological, thermal, crystalline, biodegradability, and
ecotoxicity tests. Mechanical and morphological results indicated that the
fillers' nature influences mechanical performance; all composites showed
high-tensile strength (~30 MPa) than the pristine films (~12 MPa). The use of
both fillers resulted in an interface, improving the matrix compatibility,
reflecting in good thermal performance, low-water absorption, and high hydro-
phobicity. The WA (water absorption) and hydrophobicity are essential to
maintain the crop's moisture since the water lost through plant transpiration
will be condensed and returned to the soil. Films showed biodegradability and
absence of toxicity, which allows the substitution of polyethylene commodity
films as mulching films. Biodegradation and ecotoxicity tests indicate that the
developed films are beneficial for lettuce crops and contribute to the develop-
ment of seedlings.

KEYWORDS
applications, biodegradable, biopolymers and renewable polymers

1 | INTRODUCTION common commodity polymer used. However, PE is not

The food industry is one of the most important in the
world, ranging from food production to sale to the final
consumer.1 Among the intermediate processes, there is
agriculture, which is considered an important economic
sector. Several technologies optimize crop performance
and increase productivity. Mulching films usually cover
the soil, being viable and common for plant disease con-
trol, maintaining soil temperature and humidity. This
type of films can improve the planting quality.2
The mulching plastic films global use was 7.4 million
tons in 2019,3 being the polyethylene (PE), the most
biodegradable. After the use, it turns into smaller pieces,
which form micro- and macro-plastics that aggravate the
plastics waste accumulation and terrestrial systems pollu-
tion, being an environmental issue.1,4
New alternatives have been sought due to the growing
environmental concerns that result in social and govern-
mental mobilization. Biodegradable materials have been
used to prepare mulch films, such as poly(lactic acid)
(PLA), starch, polyhydroxyalkanoates, poly(butylene
succinate-co-adipate), and poly(butylene-adipate-co-tere-
phthalate) (PBAT).5 Among these polymers, PBAT is a
synthetic aliphatic-aromatic polyester with similar

J Appl Polym Sci. 2020;e50020. wileyonlinelibrary.com/journal/app © 2020 Wiley Periodicals LLC 1 of 13

https://doi.org/10.1002/app.50020
2 of 13 de SOUZA ET AL.

mechanical and thermal characteristics than the LDPE;6,7
also, it is compostable, which makes its use a potential
alternative for commodities replacement.4
However, the use of PBAT as a mulch film has two
main limitations: its high cost, approximately 6 $ per kg,
and high sensitivity to UV radiation. To overcome this
limitation, PBAT can be blended with other biodegrad-
able polymers or filled with natural or mineral particles.8
The most common biopolymer used to blend PBAT is
brittle PLA, which guarantees excellent mechanical and
thermal performance for agriculture applications.9
Among the leading fillers used, vegetable fibers, calcium
carbonate (CaCO3), and other fillers can be cited.1,8–12
Another option, less common, is the addition of bioactive
compounds to functionalize the films. Kwiecien et al.
investigated the use of MCPA-PHBV (2-methyl-
4-chlorophenoxyacetic acid and poly(3-hydroxybutyrate-
co-3-hydroxyvalerate) to deliver herbicide to suppress
broadleaf weed growth.13 However, studies adding func-
tional agents are still rarely reported in the literature
since the addition of fertilizers or biocides could increase
the film's production costs.
This work aimed to develop a biodegradable mulch
film of PBAT/PLA blends containing different fillers:
organic compound (OC), rice husk ash (SiO2), and both.
The use of more than one-filler type and their effects in
composite films is understudied by literature. The OC
used in this work was obtained from composting indus-
tries, organic material waste from the pulp and paper
industries, the dairy industries, and the selective collec-
tion of organic waste. It is a material also used as a fertil-
izer. The studied films' properties were mechanical,
thermal, morphological, crystalline, and wettability, as
well as biodegradability. After the films' biodegradation,
ecotoxicity tests and tests in the field were performed.
organic wastes from different sources, such as paper
industries, dairy industries, and selective collection. This
material is sold as fertilizer.
2.2 | Films preparation
Initially, PBAT and PLA were mixed in the proportion
2:1 by mass; this preparation was used for the compos-
ites. For the development of all materials, a double screw
extruder was used, model AX PLASTICOS, with a diame-
ter of 20 mm and L/D = 40. The temperature profile was
135/145/148/150/150
C and 200 rpm rotation. The
extrudates were pelleted, dried, and fed in a 25 mm diam-
eter, single screw extrusion-blow film, Carnevalli model.
Table 1 presents the sample composition and nomencla-
tures, and Figure 1 summarizes the preparation of the
film. The film's thickness was 100 μm.
2.3 | Characterization
2.3.1 | Mechanical properties
The universal testing machine Instron 3367 Universal
Testing Machine (Instron Corp., Norwood, Massachu-
setts) measured the tensile tests using 10 specimens of
each formulation. Instron Bluehill software compiled the
data. The crosshead speed was 50 mm/min. Young's
Modulus (E), tensile strength (σ), and elongation at break
(ε) were determined following the ASTM D882-12
(35 x 300 x 0.1 mm). Tests were performed at ambient
conditions (25
C).
2.3.2 | Statistical analysis

2 | EXPERIMENTAL Mechanical results were subjected to one-way variance

analysis (ANOVA) by Tukey's multiple range test. The
2.1 | Materials

BASF (Germany, trade name Ecoflex) produced and sup- TABLE 1 Composition of the developed composites

plied poly(butylene adipate-co-terephthalate) (PBAT) Material (%) C1 C2 C3 C4

FBX 7011 (Mw = 51,000 g mol−1 and polydispersity index Blend PBAT/PLA 97.9 95.9 96.9 94.9
of 2.30). Nature Work (United States, trade name-
Anti-UV 0.1 0.1 0.1 0.1
IngeoTM) supplied poly(lactic acid) polymer (PLA)
2002D (Mw = 215,000 g mol−1 and polydispersity index Black carbon 2 2 2 2

of 1.9, D-isomer ~4.2%). Frenzel company (Capela de Organic compound (OC) – 2.0 – 2.0
Santana-RS, Brazil) supplied rice husk ash (RH). BASF Rice husk ash (RH) – – 1.0 1.0
(Germany) supplied carbon black (CB)-Sicopal Black Note: *The nomenclatures C1, C2, C3, and C4 were associated with
K0095 and anti-UV additive–Tinuvin. Visafertil (Mogi “composites.”
Mirim–SP, Brazil) produced the OC, which was obtained Abbreviation: PBAT/PLA, poly(butylene adipate-co-terephthalate)/
from composting industries and was prepared using polylactic acid.
de SOUZA ET AL.
F I G U R E 1 Illustrative
scheme of the preparation
method of PBAT/PLA blend and
its composites with organic
carbon (OC), rice husk ashes
(RH), and both fillers. PBAT/
PLA, poly(butylene adipate-co-
terephthalate)/polylactic acid
[Color figure can be viewed at
wileyonlinelibrary.com]
mean values were considered to be significantly different
at 95% confidence level (p ≤ 0.05).
2.3.3 | Morphological properties
The samples were cryofractured (samples were sub-
merged in liquid nitrogen, and then fractured after freez-
ing) and metalized with gold in a sputter coater Leica EM
ACE 200 (Leica Microsystems GmbH, Wetzlar,
Germany), with a 40 mA current for 60 s. The photomi-
crographs of the fractured surface samples were obtained
using a scanning electron microscope JCM-6000 (JEOL
Ltd., Akishima, Tokyo, Japan), at 10 kV acceleration volt-
age, and the images were obtained at 500x and 1000x
magnification.
2.3.4 | Thermal properties
The TGA-51 (Shimadzu) equipment performed the ther-
mal analysis, with heating from 25 to 600
C, under N2
atmosphere (50 ml min−1), using 5 mg of each sample
in platinum pans. Differential Scanning Calorimetry
(DSC) was conducted in an equipment Q1000 (DSC
Q-series [TA Instruments Inc, New Castle]), under an
N2 atmosphere (50 ml min−1), in a temperature range of
−100 to 500
C, a heating rate of 10
C min−1, in a par-
tially closed aluminum pan containing about 2 mg of
sample.
2.3.5 | X-ray diffraction
X-ray diffraction was performed on a D8 Focus diffrac-
tometer (Bruker AXS Advanced X-ray Solutions GmbH,
3 of 13
Karlsruhe, Germany) with CuKα radiation (λ =
0.15418 nm), operated at 40 kV and 40 mA. The crystal-
line structure of the polymers used as composites matrix
was evaluated by determining the peaks of the crystal-
line regions. Equation (1) estimates the crystallinity
index (CI) of composites, where Ic is the ratio of the
crystalline peak, and Ia is the amorphous halo14.
Ic
CI = × 100%: ð1Þ
Ic + Ia
2.3.6 | Water absorption
Water absorption studies were performed following the
ASTM D570-98 standard. Three specimens randomly cut
of each composition were immersed in distilled water at
room temperature. The samples were removed from the
water after specific periods (0, 0.67, 0.76, 0.82, 0.92, 1, 2,
4, 24, 48, and 167 h), wiped with a piece of cloth and
weighed in a high-precision balance, and then submerged
again in water. The weight difference calculated the
water content.
2.3.7 | Contact angle
The tests were performed according to ASTM D7334-08,
using a dynamic contact angle tensiometer (SEO) model
Phoenix 300 (Kromtech Alliance Corp., London, UK),
with three phases (air/water/sample). The static (θest)
and dynamic contact angle (θdin) were determined
according to the Young-Laplace equation observing drop-
lets of 4.00 μl during 300 s deposited in the film's surface.
The contact angle values were collected after 5 min.
4 of 13
2.3.8 | Simulated soil degradation
The simulated soil is composed of 23 wt% vegetal earth,
23 wt% organic mass, 23 wt% sand, and 31 wt% distilled
water. The simulated soil was maintained in 10–40% C:N
ratios and pH = 7.0 ± 0.5. The average soil temperature
during the tests was 27 ± 1
C, and the soil moisture con-
tent was 35 ± 2%. Five specimens of each composition
were submitted to biodegradation (ASTM D5988-12) and
monitored for 12 months by measuring the mass reten-
tion, as reported on previous works.9,15,16 The mass (%) at
the initial (ti) and final (tf) time was measured.
2.3.9 | Toxicity performance
The tests followed the OECD 208 standard (Terrestrial
plant test–Seedling Emergence and Seeding growth test).
The analysis was performed after the film's degradation
test in simulated soil. After removing all the specimens,
the soil was used to plant lettuce (Lactuca sativa). After
planting, the soil was watered daily; the number of plants
that germinate was recorded, and after 30 days, they are
harvested, and the average weights were measured. The
tests were also performed in the field.
3 | R ES U L T S A N D D I S C U S S I O N
3.1 | Mechanical properties
The mechanical tests were conducted to evaluate devel-
oped films functional properties considering the final
application; mulching films require several mechanical
stressing in the application and during the use, such as
resistance to the stress applied when spreading,
unrolling, and edge anchoring.2 Table 2 shows the
developed films mechanical results, and Figure 1
(Supplementary material) shows the characteristic
mechanical curves of all the samples. Besides, Table 1
(Supplementary material) presents the ANOVA statistical
analysis obtained for the samples to identify similarities
and differences between the samples.
TABLE 2 Mechanical results of the developed composites (elastic modulus, tensile strength, and elongation at break)
Sample Elastic modulus (E) (MPa)
C1 35.0 ± 4.0
C2 32.8 ± 1.6
C3 37.5 ± 1.4
C4 29.2 ± 0.9
de SOUZA ET AL.
According to Touchaleaume et al., mulching films
should present at least σ = 16 MPa and ε = 200%, as indi-
cated by the European standard EN 1355 (Mulching
Thermoplastic Films for Use in Agriculture and Horticul-
ture), based in the PE properties.4 Composite films
showed similar values than described in the literature.17
The blend (C1) showed good rigidity (E = 35 MPa)
and low σ (13 MPa), which occurs due to the incompati-
bility between the polymeric phases.18 The C1 mechani-
cal results were similar to those reported by Tan et al.,
that tested PE films and obtained 13 MPa and 132% for σ
and ε, respectively.19 Besides, Han and Park reported PE
films mechanical results of 15 MPa and 350% for σ and ε,
respectively, and PBAT/PLA films results of 10 MPa and
600% for σ and ε, respectively,20 indicating that our mate-
rial has the similar mechanical performance to those
reported by the literature.
C2 decreased stiffness (~7%) and increased the σ
values (25 MPa). The OC improved the films' elasticity
due to the digested organic molecules, such as proteins,
carbohydrates, oils, and other molecules that are even
aggregated in powder particles, which can interact with
the PLA phase, improving the mechanical resistance.21,22
The literature commonly reports that PBAT composites
with natural compounds have low compatibility due to
the polarity difference.23,24 The use of blends with PLA
was beneficial in the present work, increasing the matrix-
reinforcement interactions, reflecting in increases in ten-
sion and a slight decrease in the composite's stiffness.
Similar results were obtained for C3, with an increase in
the rigidity (E = 37 MPa) and a significant decrease in
the composites' ductility (ε = 110%) after the RHs
addition.
The observed differences between samples C2 and C3
can be attributed to the fillers' nature and chemical struc-
tures. OC is organic, natural, and amorphous,25 and its
chemical structure are mainly composed of carbon atoms
bonded via covalent bond with other carbon or hydrogen,
oxygen, nitrogen, phosphorus, and halogens.26
Considering OC chemical properties, it is expected
good interactions with the PBAT/PLA matrix; however,
its low crystallinity slightly decreased the stiffness and
improved the elongation at break. The RH is an inorganic
Tensile strength (σ) (MPa) Elongation at break (ε) (%)
12.9 ± 6.0 210.2 ± 39.0
25.3 ± 5.0 217.0 ± 65.0
24.3 ± 1.0 188.3 ± 20.0
37.5 ± 1.0 110.0 ± 36.0
de SOUZA ET AL.
and semi-crystalline compound, containing substantial
amounts of carbon, amorphous silica, and other mineral
compounds.25,27 The RH has a large structure limiting
the molecular chains' interaction, resulting in lower σ
and inducing the break under tension, reflecting in low-ε
values. Besides, RH chemical structure and morphology
result in high-composites stiffness, as reported by You
et al.28
In the C4 sample, both fillers reduced the stiffness
(E = 29 MPa) and improved the tensile strength
(37 MPa). The fillers' combination decreased the compos-
ite's stiffness, probably because the polymers and fillers
are not compatible.2 Also, the stiffness decrease can be
attributed to defects or agglomerations, inducing voids
formation.29 However, the tensile strength showed excel-
lent values due to the new interface that leads to better
adhesion and properties.30 Besides, the σ increase can be
attributed to an irregular filler distribution into the
matrix that improve the chain entanglements and reflects
in higher tensile strength.29 The reported results showed
significant technological importance and were superior
to innumerous articles, such as França et al. and Han
et al.12,20 Other authors also reported composites with
superior mechanical properties than the neat films for
mulching applications, such as Ayu et al. and Oliveira
et al.8,31
Considering the European standard EN 1355, the ten-
sile strength is an essential mechanical parameter evalu-
ated for mulching films. Therefore, the C4 and C1
samples were the most adequate.
3.2 | Morphological properties
Figure 2 corresponds to SEM images of the cross-section
of the film. Figure 2(a) shows the neat blends, and it is
possible to identify the biphasic nature of this system,
with two incompatible phases and heterogeneous sur-
faces.32,33 To the right of the images it is presented an
illustration of the two immiscible phases, where the pink
represents the PBAT phase and the blue, the PLA phase.
However, despite being immiscible, the blend developed
presented a different morphology from that reported by
the literature; no PLA fibers, spheres, or agglomerates
were observed in the blends.34–36 However, the lamellae
morphology can be attributed to this incompatibility. No
particles were observed in the neat blend since the CB is
at the nanoscale.
Figures 2(b)-(d) show the composites' SEM images.
The addition of OCs resulted in several voids in the poly-
meric structure and a smooth surface, indicating a ductile
fracture surface and that some fibers were pulled out dur-
ing the cryofracturing process, indicating poor
5 of 13
adhesion.37 The C3 film (Figure 2(c)) exhibited a coarser
and fragile fracture surface,38 corroborating the mechani-
cal results. This sample also shows a large number of
agglomerates, which justifies the low ductility of this
sample.
Figure 2(d) shows the PBAT/PLA blend with both
fillers. Both fillers addition improved polymers' miscibil-
ity and decreased the presence of the voids due to the CO
and RH dispersion, creating an interface between PLA
and PBAT phases. This interface is possible because the
functional groups of PLA and PBAT, which in the pure
blend did not interact, start to physically interact with
the reinforcing agents, forming a cross-linked network
that reflects in the increase in the values of tensile
strength and more homogeneous morphology of the
films.32,33 This behavior is very positive and justifies the
importance of the joint use of both fillers.
3.3 | Thermal properties
The thermogravimetric analysis (TGA) technique
assessed the thermal stability of the composites.39
Figure 3(a) shows the acquired thermograms and
Figure 3(b) for their respective DTGs. Figure 2S shows
the thermograms of all the pristine materials, i.e., PLA,
PBAT, Anti-UV, OC, and RH. Comparing the Tonset of
the blend and neat polymers, it was observed that the
blend showed an intermediary thermal behavior between
the PBAT and PLA, as expected. For the C1 (neat blend),
the decomposition measured by Tonset indicates the
decomposition at 316.4
C, and Tmax is ~397
C. The cur-
ves were similar up to 300
C, even for the composites;
possibly, the reinforcements obtained good dispersion
and covering by the polymer chains during the extrusion
processing. Two events of weight loss were observed for
all the samples: at ~400
C and ~ 450
C. The first one is
attributed mainly to PBAT and PLA degradation,40,41 and
the second attributed CB and other industrial additives.42
The C2 and C3 samples showed a slight decrease on
Tonset and Tmax values, which is a consequence of the cat-
alytic effect of fillers in ester bond polymerization, that
favors the formation of free radicals and reactive and
groups during polyesters decomposition.9 Considering
the OC, this filler contains only organic matter, which
has thermal decomposition at temperatures lower than
polymers.31,36 The rice husk ashes (SiO2) are stable com-
pounds and did not influence the thermal stability.43,44
Briefly, the slight changes are attributed to the fillers
hydrophilic character, and only changed the thermal deg-
radation first step.
Different from the expected, C4 presented a similar
thermal behavior when compared to C1, with slight
6 of 13 de SOUZA ET AL.

F I G U R E 2 SEM images (500 and 1000x magnification) of (a) PBAT/PLA films (C1) and its composites with (b) organic compound
(C2), (c) rice husk ashes (C3), and (d) both fillers (C4). OC, organic carbon; PBAT/PLA, poly(butylene adipate-co-terephthalate)/polylactic
acid; RH, rice husk ashes [Color figure can be viewed at wileyonlinelibrary.com]

FIGURE 3
(a) Thermogravimetric curves
for PBAT/PLA and its
composites, and (b) DTG curves.
PBAT/PLA, poly(butylene
adipate-co-terephthalate)/
polylactic acid [Color figure can
be viewed at
wileyonlinelibrary.com]

increases in thermal stability, indicating possible compat- interaction between the particles and the formation of a
ibility between the mixtures and polymeric matrix.45 This filler network between OC and RH.42 The ashes were not
enhancement can be explained by possible weak physical investigated because the material's thermal behavior after
de SOUZA ET AL.
420
C is unexpected and can be attributed to an equip-
ment problem.
Figure 4 shows the DSC curves of PBAT/PLA and its
composites. The curves show two distinct endothermic
peaks, where Tm1 is attributed to PBAT melting
(~120
C), and Tm2 to PLA melting (~150
C).46
Table 3 shows Tg and Tm values, and composites
slightly decrease the Tg PLA, which can be attributed to
the higher chain mobility of PLA molecules in the
films.47 This greater mobility is associated with the need
to reorganize and distribute the molecules around the
fillers and a greater tendency to slip the PLA chains that
physically interacted with OC and RH.
The double melting peaks of PLA at ~150
C are
attributed to lamellar rearrangement during PLA crystal-
lization. However, the composites showed only a single
peak, since the fillers changed the recrystallization pro-
cess and the crystallite domains,48 without significant
variations in the transition temperatures. The Tm2 peak
change indicates that there was a good interaction
between reinforcement and matrix, without the presence
of additional phases.
F I G U R E 4 DSC thermograms of all the studied composites.
DSC, differential scanning calorimetry [Color figure can be viewed
at wileyonlinelibrary.com]
T A B L E 3 DSC results were obtained from the DSC graphs,
and the main parameters are Tg PLA, Tm1 PBAT, and Tm2 PLA
Sample Tg PLA (
C) Tm1 PBAT (
C) Tm2 PLA (
C)
C1 61.9 122.7 154.8
C2 61.7 121.3 156.4
C3 61.4 122.3 154.9
C4 61.4 120.7 155.6
Abbreviations: DSC, differential scanning calorimetry; PBAT/PLA,
poly(butylene adipate-co-terephthalate)/polylactic acid.
7 of 13
3.4 | X-ray diffraction
Figure 5 shows the X-ray diffractograms of PBAT/PLA
and its composites, and Figure 3S (Supplementary Mate-
rial) shows the XRD graphs of pristine PLA and PBAT.
Figure 5(a) shows the PBAT/PLA blend and indicated
peaks at 19, 23.6, 28.7, and 29.6
, attributed to (002) plane
of CB, (230) plane of PLA, and (200) plane of CB.42
Besides, the Figure 5(a) insert shows a peak at ~24.5
,
attributed to the PBAT crystal structure.47
Sample C2 showed similar diffraction peaks that C1,
which was reported in the literature for composites with
biomass reinforcing PBAT or PLA films.37,49–51 Sample
C3 showed a different XRD profile, with new peaks at
36.1, 39.5, 43.3, and 47.7
, attributed to SiO2 and other
components of RHs.52–54 The increase in the amorphous
region of 20–28
is associated with amorphous silica,
characteristic of RH. Besides, it was observed a peak shift
of 24 to 23
, attributed to the possible interaction
between PBAT and the filler.
The C4 diffractogram showed a similar profile of sam-
ples C2 and C3, corresponding to the mixture.
3.5 | Water absorption and wettability
The water immersion test investigated the hygroscopicity
of all samples. Figure 6(a) shows changes in water
absorption of the PBAT/PLA sample and its composites.
All samples show rapid absorption on the first day, and
after that, it was reached a plateau.55 The fillers addition
separately increased the water absorption, from 1.25 to
1.32%, due to their hydrophilic nature, voids, and micro-
cracks that could be formed in the structure.56 However,
the addition of both fillers decreased the film's water
absorption to 1.22%. According to Ren et al., the low-
water absorption of the films is due to the PLA phase,
hydrophobic, which has a crystalline behavior and limits
the water diffusion through the films.57
Considering the C4 sample, as discussed in the
mechanical tests, there was an increase in the miscibility
of in the polymers' miscibility and good dispersion. Possi-
bly the water absorption decreased because the func-
tional groups present in the films interacted with each
other, decreasing the available free hydroxyls, hydro-
philic groups that influence the water absorption.
Besides, the fillers probably occupied the free spaces of
the films.9
The two significant roles played by mulching films are
increasing soil temperature and maintaining soil moisture
by reducing water evaporation.4 According to Kasirajan
and Ngouajio, evaporation can be reduced depending on
the type of mulching film.58 In our case. The low-water
8 of 13
F I G U R E 6 (a) Water absorption curve of the composites and
(b) contact angle results [Color figure can be viewed at
wileyonlinelibrary.com]
absorption is essential in mulching films to maintain the
crop's moisture since the water lost through plant transpi-
ration will be condensed and returned to the soil.4,14 So,
the developed films have the potential to be applied as a
mulching film for different crops.
de SOUZA ET AL.
F I G U R E 5 XRD
diffractogram of the studied
composites: (a) C1, (b) C2,
(c) C3, and (d) C4. XRD, X-ray
diffraction [Color figure can be
viewed at
wileyonlinelibrary.com]
The film's wettability is an intrinsic characteristic of
each material. Mulch films generally have good moisture
retention ability.2 Contact angle measurements assessed
this property of PBAT-PLA films. PBAT/PLA blend
showed a contact angle of 72.2
(Figure 6(b)), similar to
those reported in the literature.2,59 Therefore, the addi-
tion of fillers significantly increased the contact angle
(up to 82
), that is, hydrophobicity.60 As discussed before,
this might be due to the formation of hydrogen bonding
between hydroxyl groups of the fillers and of the PLA, or
carboxyl groups of PBAT, thereby resulted in the reduc-
tion of hydrophilicity of the films.61 Samples C3 and C4
show the most appropriate behavior to act as mulch film,
compared to commercial PE films.62
The contact angle submits the sample to 5 min in
contact with water, while the water absorption immerses
the samples and maintains for 170 h. So, the influence of
time and morphology determines how much the film can
absorb water since the PBAT/PLA blend has free spaces
for swelling of the studied systems. 9
3.6 | Simulated soil degradation
Figure 7 shows the biodegradation of the studied film
considering weight loss during tests into simulated soil,
and Figure 4S shows the biodegraded polymers visual
de SOUZA ET AL.
F I G U R E 7 Weight loss (%) measured during biodegradation
into soil simulation [Color figure can be viewed at
wileyonlinelibrary.com]
aspects. The biodegradation process occurred in two
stages: (i) increase of the initial mass due to the swelling
of the polymer and formation of biofilm,63 and
(ii) decrease of the mass due to the hydrolysis (abiotic
process) and biotic process (transformation of the films
into biomass, CO2, and H2O).15,18,64
Although PBAT and PLA being considered compost-
able polymers (i.e., adequate conditions of light, humid-
ity, temperature, and correct amount of microorganisms
decompose), the literature also reported these materials
as soil biodegradable. According to Weng et al., the PBAT
and PLA biodegradation rates in the blend are low than
the neat polymers due to the different chain entangle-
ments and polymers organization.65 In this work, it was
found that only after 200 days, the samples show a
F I G U R E 8 (a) Digital images of ecotoxicity tests with lettuce and (b) germination index after 10 days [Color figure can be viewed at
wileyonlinelibrary.com]
9 of 13
decrease in mass (effective biodegradation), and after
1 year of testing, the samples lost approximately 50% of
the weight. According to Palsikowski et al., the PLA addi-
tion is much less degradable than neat PBAT due to PLA
hardly biodegradability in the glassy state.18 Even with
this slow degradation rate, more than 50% of the mass
was transformed into biomass, CO2, and water in 1 year,
making the material highly biodegradable.4 Rocha et al.
prepared PBAT/PLA/CaCO3 films and observed only 2%
weight loss, attributed to low-water absorption and
hydrolysis.9
However, it is essential to note that in soil, due to var-
iable climatic conditions, biodegradation can occur at
variable times. This test demonstrated that the prepared
films are biodegradable, that is, samples buried in soil
rich in moisture, oxygen, and nitrogen, have the potential
to transform into biomass and low-molar mass compo-
nents over time. Also, soils rich in microbiota can accel-
erate the biodegradation process.66 However, the field
biodegradation test was not performed. The main objec-
tive of biodegradable mulch films is to obtain a film that
can be discarded in soil and will gradually degrade,
avoiding final disposal costs, and reducing environmental
impacts associated to the use of PE mulch films, usually
applied in this process.9
3.7 | Toxicity performance
During the biodegradation process, polymers can release
substances from the degradative process, affecting plant
germination and growth. The soil used to biodegrade the
films were used to perform ecotoxicity tests in the labora-
tory with lettuce germination. Figure 8(a) shows the
10 of 13
digital images of the tests, and Figure 8(b) shows the let-
tuce germination index after 10 days. Lettuce is a highly
sensitive and widely available culture for this type of
test.67 Germination was affected only by the compounds
generated after C3 biodegradation; other samples showed
an improvement on this parameter. Germination is a pro-
cess that occurs after the seeds bury. This process
involves the mobilization of the food reserves stored in
the endosperm, ending with the emergence of the radicle
through the seed coat. 67,68 Since germination is
FIGURE 10 Illustration of monitoring of plants growth, performed weekly [Color figure can be viewed at wileyonlinelibrary.com]
de SOUZA ET AL.
dependent on the availability of food for plant growth,
and it was found that the C4 sample was the most appro-
priate considering nutrient bioavailability, resulting in a
higher germination rate. These results can be attributed
to the synergic effect of both fillers during the biodegra-
dation. C4 films can be left in the soil and served as food
for the next crops after use. In C4, considering that the
RH did not affect the germination positively, it is possible
to infer that the OC was responsible for the results since
this material are fully constituted of organic matter that,
F I G U R E 9 (a) Lettuce
dried mass after 4 weeks of tests
and (b) digital images of dried
samples [Color figure can be
viewed at
wileyonlinelibrary.com]
de SOUZA ET AL.
in anaerobic digestion, degrades 60–70%, resulting in
high oxygen, nitrogen, and carbon molecules in the
soil.25 Since the germination depend on soil quality and
nutrients availability, the C4 biodegradation resulted in
the soil is the richest and with high potential for lettuce
germination and growth.
After 4 weeks of planting, the lettuces were harvested
and dried to assess their mass (Figure 9). Similar to the
trend observed for germination, it was found that the
seedling masses were higher for the C4 film, which
means that the soil proved to be more apt for plant
growth.
The developed films differ when compared to tradi-
tional PE mulching films in composition and final
wastes. PE films are prepared with various additives and
plasticizers that migrate during application to the surface
and come into contact with the plant or the soil,
compromising its quality and safety.68–70 The developed
films do not have plasticizers and toxic additives, having
natural fillers and CB as anti-UV.
Since the results of the characterizations, biodegrada-
tion, and ecotoxicity indicate that C4 films are the most
suitable for application as mulching films, field tests were
carried out with this sample to verify its influence on
F I G U R E 1 1 Representa-
tive schematic representation of
the main results of the
developed films considering its
application as mulching films
for lettuce crops [Color figure
can be viewed at
wileyonlinelibrary.com]
11 of 13
lettuce growth. These final tests validated the efficiency
of the C4 sample as mulch film and tested in a site with
30 meters long and 1.6 meters wide. The evaluation of
the curly lettuce's growth was performed visually and
weekly, and the final assessment was performed after
1 month and 25 days (Figure 10). The mulch films good
performance in lettuce growth can be attributed to the
RH, which contains SiO2 to be absorbed by the plant and
deposited on the leaves, protecting them from the insects'
attack. At the end of the tests, the lettuce stem bore was
17.2 ± 2.2 mm, while the values for PE mulching films,
tested as a standard formulation, are 13.2 ± 1.7 mm. The
mass of lettuce produced in 1 linear meter of the site was
2.25 kg for the C4 sample, while the PE production was
1.7 kg, and the weight of 30 linear meters was 67.5 for let-
tuce protected with C4 mulching film, while the plants
using PE mulching films was 51 kg.
These results indicate the relevance of the devel-
oped composite, and its use increases the quality and
quantity of lettuces produced using the films as a soil
cover. Besides, there is a reduction in costs associated
with the removal of nonbiodegradable films and their
disposal, being economically and ecologically more
viable.
12 of 13
Figure 11 summarizes the main results obtained in this
manuscript considering the final application of PBAT-PLA
mulching films reinforced with RHs and an OC.
4 | C ON C L U S I ON S
This study prepared biodegradable PBAT-PLA compos-
ites mulch films containing two different fillers: RH and
OC via melting extrusion, and the fillers were investi-
gated separately and together. Mechanical and morpho-
logical results indicated that the fillers' nature influenced
the mechanical performance; all composites showed
high-tensile strength (~30 MPa) than the pristine films
(~12 MPa). The use of both fillers improved the matrix
compatibility, reflecting in superior mechanical proper-
ties and thermal stability maintenance. The continuous
composites phase decreased the void's presence, and the
water absorption, which is interesting for mulching films
to maintain the crop's moisture since the water lost
through plant transpiration, will be condensed and ret-
urned to the soil. Biodegradation tests indicated that the
samples could biodegrade after 6 months, and the fillers
accelerate the composites biodegradation. Considering
ecotoxicity tests, the composites with both fillers were the
most appropriate considering nutrient bioavailability,
resulting in a higher germination rate and, after 4 weeks,
the higher dried lettuce mass. The field tests indicated
growth in lettuce yield production using the developed
mulching films when compared to neat PE films. The let-
tuce mass-produced 30 linear meters was 67.5 kg for let-
tuce protected with C4 mulching film, while the plants
using PE mulching films was 51 kg. Our results indicate
that the use of the developed films is promising for soil
coverage applications, in addition to reducing costs of
mulching films removal and discard.
A C K N O WL E D G M E N T S
This research was funded by CNPq (#305819/2017-8, and
#306401/2013-4) and FAPESP (#2018/11277-7). The
authors thank the UFABC, CAPES (Code 001),
REVALORES Strategic Unit, and Multiuser Central
Facilities (CEM-UFABC). The authors thank the compa-
nies: BASF, Visafertil, Frenzel, Thermoblend, and
Cromex for providing the samples.
ORCID
Derval S. Rosa https://orcid.org/0000-0001-9470-0638
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SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: de Souza AG,
Ferreira RR, Harada J, Rosa DS. Field performance
on lettuce crops of poly(butylene adipate-co-
terephthalate)/polylactic acid as alternative
biodegradable composites mulching films. J Appl
Polym Sci. 2020;e50020. https://doi.org/10.1002/
app.50020