materials

Article
Development of Biodegradable PLA/PBAT-Based Filaments for
Fertilizer Release for Agricultural Applications
Thyago Camelo Pereira da Silva 1 , Allef Gabriel da Silva Fortes 1 , Iago Rodrigues de Abreu 1 ,
Laura Hecker de Carvalho 2 , Yeda Medeiros Bastos de Almeida 3 , Tatianny Soares Alves 1, * and Renata Barbosa 1

1 Graduate Program in Materials Science and Engineering, Technology Center, Federal University of Piauí,
Teresina 64049-550, PI, Brazil
2 Center Science and Technology, Graduate Program in Materials Science and Engineering, Federal University
of Campina Grande, Campina Grande 58428-830, PB, Brazil
3 Center for Technology and Geosciences, Graduate Program in Chemical Engineering, Federal University of
Pernambuco, Recife 50670-901, PE, Brazil
* Correspondence: tatiannysoares@[Link]

Abstract: The aim of this work was to produce filaments of PLA/PBAT and NPK fertilizer adsorbed
on organophilized bentonite intended for application in the prototyping of biodegradable agricultural
artifacts in 3D printing, using the Fused Deposition Modeling (FDM) technique. This is the first time
that we have reported this composite for a 3D printing approach. Systems containing PLA/PBAT,
organobentonite and NPK were initially processed in an internal mixer and later extruded as filaments
in a single-screw extruder. The prototypes were printed by FDM. Structural, morphological and
thermal properties, as well as NPK releasing, were investigated. The results suggest that exfoliated
and/or intercalated nanocomposites were obtained by the organoclay addition to the PLA/PBAT
Citation: da Silva, T.C.P.; Fortes, blend. The morphological analysis revealed a good surface quality of the impressions. Systems
A.G.d.S.; de Abreu, I.R.; de Carvalho, containing organobentonite released approximately 22% less fertilizer in 24 h compared to the systems
L.H.; de Almeida, Y.M.B.; Alves, T.S.; without organobentonite. This difference is due to the higher concentration of nanoparticles that
Barbosa, R. Development of generate more barriers to the diffusion of NPK. The release data for these systems had a better fit
Biodegradable PLA/PBAT-Based to the kinetic model of Korsmeyer-Peppas. Thus, studied filaments have the potential to retard the
Filaments for Fertilizer Release for release of fertilizer and are suitable for further development of structures for agricultural applications
Agricultural Applications. Materials by FDM.
2022, 15, 6764. [Link]
10.3390/ma15196764
Keywords: controlled release; nanocomposites; 3D printing; biodegradable
Academic Editors: Fouad Laoutid
and José-Marie Lopez-Cuesta

Received: 12 August 2022

1. Introduction
Accepted: 26 September 2022
Published: 29 September 2022 The world agricultural industry uses significant amounts of mineral fertilizers. The
world agricultural demand for NPK (mixed mineral fertilizer based on nitrogen—N,
Publisher’s Note: MDPI stays neutral
phosphorus—P and potassium—K) forecast for 2022 is of the order of 200 thousand tons
with regard to jurisdictional claims in
and an expected CAGR of 5.0% by 2028 [1,2]. The continent of greatest demand is Asia,
published maps and institutional affil-
due to factors such as economies focused on agriculture, large areas that allow cultivation
iations.
and high population density, which requires greater productivity of agricultural crops.
For example, China and India rank second and third in urea consumption, respectively.
However, this high demand comes at a cost, due to the unregulated application of these
Copyright: © 2022 by the authors. types of fertilizers, nutrient loss can occur, as indicated by Singh et al. (2021), where India
Licensee MDPI, Basel, Switzerland. had a negative balance of approximately 8 to 10 MT year−1 , and the situation is expected to
This article is an open access article worsen, reaching 15 MT year−1 [2–4]. Furthermore, traditional NPK-type fertilizers have
distributed under the terms and significant polluting potential, resulting from volatilization losses which generate atmo-
conditions of the Creative Commons spheric pollution and leaching of oxidized nutrients, which in turn contaminate aquifers.
Attribution (CC BY) license (https:// The use of fertilizers with controlled or slow release (CRF) stand out among the recent
[Link]/licenses/by/ solutions studied to mitigate these impacts [5–7].
4.0/).

Materials 2022, 15, 6764. [Link] [Link]

Materials 2022, 15, 6764 2 of 13

CRFs reduce losses by delivering nutrients more efficiently as they are designed
to release active fertilizer compounds in a delayed or controlled manner, in line with
the specific nutrient uptake needs of plants [8]. In general, CRFs are produced from
the encapsulation of agrochemical macro- and micronutrients, such as urea or NPK, by
structures that control the diffusion of water, gases and the release of the active agent [5,9].
Biodegradable polymers stand out among the materials used for the encapsulation
or in the distribution of the active agent dispersed in it. The use of biodegradable poly-
mer matrices, such as poly(hydroxybutyrate) (PHB) [10–13], poly(lactic acid) (PLA) [14],
starch [15–17], lignin [18], carboxymethyl cellulose [19] and chitosan [20,21], is doubly
advantageous because during their microbial degradation, nutrients are released with
greater control in the environment, minimizing losses and reducing the accumulation of
residues in the soil in a sustainable way.
Allied to the use of biodegradable plastics for sustainability, industry 4.0 presents
itself as a crucial tool in increasing productivity and efficiency in the planning and control
of products in several segments, with agricultural development being the most recent.
Additive manufacturing, one of the pillars of this new industry, comprises a low-cost,
efficient, easy-to-operate production technique which provides a wide variety of materials
that can be used in versatile applications [22–24] ranging from biomedical, automotive and
aerospace applications as well as prototyping industries in general [25].
In recent years, 3D printing has been used in drug delivery applications, such as in
the manufacture of tablets and in the manufacture of dressings containing active pharma-
ceutical substances [26]. This technology potentially can be applied in the development of
agricultural artifacts, traditionally produced by other processing means, as well as enable
the production of systems with biodegradable polymer matrices to control the release
of fertilizers.
The association of biodegradable matrices with inorganic nanoparticles is an inter-
esting alternative to improve the performance of CRFs. A polymer matrix with potential
for application in controlled release and association with nanoparticles is Ecovio® , a com-
mercial biodegradable thermoplastic blend produced by BASF. Ecovio® is composed of
PLA and poly(butylene adipate co-terephthalate) (PBAT) (Ecoflex® ) and is a material with
mechanical properties similar to those of traditional polymers used for agricultural applica-
tions [27,28]. Organophilic bentonite clays stand out among the inorganic nanoparticles
applicable to the adsorption of fertilizers and their CRF biodegradable nanocomposites have
greater matrix stability which allow for the slow release of agricultural compounds [5,29].
In addition to controlling drug release, nanoparticles can provide improvements in general
properties of the composite, such as tensile strength, elastic modulus, flexural strength,
flexural modulus [30,31], barrier properties [32] and thermal stability [33]. These improve-
ments expand the application possibilities of these systems and may even result in materials
with suitable characteristics for application in the production of planting artifacts with
high added value, such as fertilizer sticks, biodegradable tubes and soilless agriculture
substrates able to release nutrients.
Therefore, the present work aims to develop PLA/PBAT nanocomposite filaments,
in which the organophilic bentonite clay filler is incorporated with NPK fertilizer, to be
used in Fusion and Deposition Modeling (FDM) prototyping of biodegradable agricultural
artifacts capable of releasing nutrients. To the best of our knowledge, this is the first time
that a sustainable bio-based nanocomposite filament for a 3D printing approach capable of
releasing fertilizer with the potential to be applied in several innovative planting techniques
is reported.

2. Materials and Methods

2.1. Materials
The PLA/PBAT blend, commercially known as Ecovio® , grade F2224, supplied by
BASF S/A (Camaçari, BA, Brazil) with a density of 1.24–1.26 g/cm3 and composed of 45%
PLA and 55% PBAT, was used as polymeric matrix. The organophilized montmorillonite
 Materials 2022, 15, x FOR PEER REVIEW 3 of 15

Materials 2022, 15, 6764 3 of 13

2. Materials and Methods
2.1. Materials
The PLA/PBAT blend, commercially known as Ecovio , grade F2224, supplied
® by
clay used as a filler and fertilizer carrier was commercial bentonite Cloisite 20A® (South-
BASF S/A (Camaçari, BA, Brazil) with a density of 1.24–1.26 g/cm³ and composed of 45%
ern Clay Products Inc., Gonzales, TX, USA), particle size < 10 µm, basal spacing (XRD,
PLA and 55% PBAT, was used as polymeric matrix. The organophilized montmorillonite
d001): 2.7 [Link]
Asused
fertilizer,
as a filleraand
mixed mineral
fertilizer carriercompound
was commercialwasbentonite
used, NPK 4-14-8
Cloisite with 4%
20A® (Southern
monoammonium phosphate
Clay Products Inc.,or ammonium
Gonzales, dihydrogen
TX, USA), phosphate
particle size (MAP)
< 10 μm, basal (NH
spacing 4 H2 PO
(XRD, 4 ),
d001):
14% simple superphosphate
2.7 nm. As fertilizer,(P2 Oa5 +mixed
Ca + mineral
S) and 8% potassium
compound was chloride
used, NPK (KCl), produced
4-14-8 with 4%
monoammonium
by Fertilizantes Tocantins S/A phosphate
(São Luís,or ammonium
MA, Brazil). dihydrogen phosphate (MAP) (NH4H2PO4),
14% simple superphosphate (P2O5+Ca+S) and 8% potassium chloride (KCl), produced by
Fertilizantes
2.2. Preparation Tocantins
of Composites S/A (São Luís,
and Production MA, Brazil).
of Filaments
A schematic illustration
2.2. Preparation of preparation
of Composites of composites,
and Production production of filaments and 3D
of Filaments
printing of the samples is shown in Figure 1. Concentrates
A schematic illustration of preparation of composites, wereproduction
preparedofinfilaments
a Haake™ and
Rheomix 30003D(Thermo Fisher Scientific, Waltham, MA, USA) internal mixer
printing of the samples is shown in Figure 1. Concentrates were prepared in a Haake™ fitted with
roller-type rotors coupled
Rheomix 3000 to a torque
(Thermo rheometer
Fisher Scientific,operating
Waltham, MA,at 180 ◦ C internal
USA) and 60 mixer
rpm, for 8 min
fitted with
roller-type
(Figure 1a). During rotors coupled
processing, aftertothe
a torque
meltingrheometer
of Ecovio ® , identified
operating at 180 °Cbyandthe
60 stabilization
rpm, for 8 min
of torque after(Figure 1a). During
an average timeprocessing,
of 4 min, after
NPKthe melting of Ecovio®clay
and bentonite , identified
were by the stabilization
simultaneously
of torque after an average time of 4 min, NPK and bentonite clay were simultaneously
added. Subsequently, the concentrates were diluted to obtain the filaments for 3D printing
added. Subsequently, the concentrates were diluted to obtain the filaments for 3D printing
in an AX-16 (AX Plásticos, Diadema, SP, Brazil) single-screw extruder, with 16-millimeter
in an AX-16 (AX Plásticos, Diadema, SP, Brazil) single-screw extruder, with 16-millimeter
screw diameter (L/D = 26),(L/Doperating with a temperature profile of 150, 155155
and 155 ◦ C in
screw diameter = 26), operating with a temperature profile of 150, and 155 °C in
its three heating zones
its three and screw
heating speed
zones and screwofspeed
30 rpm (Figure
of 30 1b). Filament
rpm (Figure compositions
1b). Filament compositionsare are
summarized in Table 1. in Table 1.
summarized

Figure [Link]
Figure 1. Schematic Schematic illustration of: (a) preparation
of: (a) preparation of concentrates;
of concentrates; (b)(b)production
production ofoffilament; (c)
filament;
prototype printing.
(c) prototype printing.
Table 1. Filament compositions.
Table 1. Filament compositions.
Identification Bentonite (% w/w) NPK (% w/w)
Identification Ecov -
Bentonite (% w/w) -
NPK (% w/w)
Ecov/3NPK - 3
Ecov - -
Ecov/3Bent 3 -
Ecov/3NPK - 3
Ecov/3Bent 3 -
Ecov/6Bent 6 -
Ecov/3Bent/3NPK 3 3
Ecov/6Bent/3NPK 6 3
Legend: Ecov = Ecovio® , Bent = Cloisite 20A® , organophilic bentonite.

Filament dimensions were controlled in a FTR1 pulling system (Filmaq3D, Curitiba,

PR, Brazil) and a winding tool (FE1, Filmaq3D, Curitiba, PR, Brazil) (Figure 1b). Pulling
parameters were adjusted by changing the rotation speed of the winder roll, initially set at
35 rpm, in order to produce filaments with diameters close to 1.75 mm. Filament diameters
were measured with a Digital Caliper® (0–150 mm) and presented in Table 2.
Materials 2022, 15, 6764 4 of 13

Table 2. Filament diameters.

Identification Diameter (mm)

Ecov 1.75 ± 0.05
Ecov/3NPK 1.74 ± 0.07
Ecov/3Bent 1.76 ± 0.06
Ecov/6Bent 1.75 ± 0.08
Ecov/3Bent/3NPK 1.77 ± 0.07
Ecov/6Bent/3NPK 1.77 ± 0.08

2.3. Prototype Printing

Thin-walled tubular prismatic specimens (20 × 20 × 20 × 1 mm) were obtained with
a 3D printer Da Vinci® 1.0 Pro. (XYZprinting Inc., New Taipei City, Taiwan) with a 0.2-
millimeter print nozzle (Figure 1c). The printing parameters defined in the preliminary
tests to determine the ideal processing conditions of the filaments by FDM are summarized
in Table 3.

Table 3. Filament printing parameters.

Filling Density No filling

Higher and Lower Layers 0
Number of Walls 2
Printing Speed 30 mm/s
Travelling Speed 50 mm/s
Printing Temperature 170 ◦ C
Print Table Temperature 45 ◦ C
Filament Diameter 1.75 ± 0.10 mm

2.4. Characterization
The morphology of the printed surfaces was analyzed by scanning electron microscopy
(SEM) in a TESCAN VEGA 3 instrument (TESCAN ORSAY HOLDING, a.s., Brno, Ko-
houtovice, Czech Republic). X-ray diffractometry (XRD) was performed on samples from
the walls of the printed specimens on a Shimadzu X-ray diffractometer (LABX-XDR 600,
Shimadzu, Kyoto, Japan), operating in the angular range from 2◦ to 40◦ (2θ), with a speed
of 2◦ /min and a power of 40 kV/30 mA, with incident radiation Cu-Kα (λ = 1.5406 Å).
Thermogravimetric analyses (TGA) were carried out in an equipment Mettler-Toledo Ind.
e Com. (Barueri, SP, Brazil), under nitrogen atmosphere with a flow of 50 mL·min−1 from 0
to 600 ◦ C and a heating rate of 10 ◦ C·min−1 .

2.5. Release Rate in Water and Release Kinetics

The release profile of NPK salts from the filaments was indirectly determined by mea-
suring the total concentration of electrolytes in solution by ionic conductivity in deionized
water using a portable conductivity meter (MB-11P, Marte Científica, Santa Rita do Sapucaí,
MG, Brazil), according to the procedure described by Daitx et al. (2019) [10] and Scaffaro,
Citarrella and Gulino (2022) [34]. Average values of triplicate measurements, performed
at room temperature, are reported. The NPK content released was calculated with the
following Equation (1):
Vs ∑1n−1 Ci +V0 Cn
Ar = ×100 (1)
V0 C t
where Ar is the percentage of NPK released (%), Vs is the sample volume (mL), Ci and Cn
are the conductivities of the samples (µS cm−1 ) at time i through n, V0 is the initial test
volume (mL) and Ct is the theoretical total conductivity (µS cm−1 ). The theoretical total
conductivity value was based on the free NPK content released in deionized water.
The rate release of the systems and their physical kinetics mechanism were determined
by comparing the release data with zero-order and first-order mathematical models and
the Higuchi and Korsmeyer-Peppas models [35–37].
Materials 2022, 15, 6764 5 of 13

3. Results and Discussion

3.1. Morphological Analysis
The morphological analysis of the composites was performed by SEM of the external
surfaces of the printed specimens. Figure 2 shows that the external surfaces of the matrix
and composites taken at 50× magnification have good quality as there was no formation
of voids and agglomerates. There is no apparent porosity and there was no substantial
change in the interlayer adhesion with the addition of NPK and bentonite. For the 200×
magnifications,
Materials 2022, 15, in Figure 2b*–d*, some agglomerates are observed, characteristic of the clay
x FOR PEER REVIEW 6 of 15
particulate fillers and NPK fertilizer used [38].

Figure 2. SEM micrographs of the external surface of a 3D printed sample for different compositions
Figure 2. SEM micrographs of the external surface of a 3D printed sample for different compo-
and magnifications: 50× [(a) Ecov, (b) Ecov/3NPK, (c) Ecov/3bent, (d) Ecov/6bent, (e)
sitions and magnifications: 50× and
Ecov/3Bent/3NPK [(a) (f)
Ecov, (b) Ecov/3NPK,
Ecov/6bent/3NPK]; 200× (c)
[(a*)Ecov/3bent, (d) Ecov/6bent,
Ecov, (b*) Ecov/3NPK, (e)
(c*) Ecov/3bent, (d*)
Ecov/3Bent/3NPK and (f) Ecov/6bent/3NPK];
Ecov/6bent, (e*) Ecov/3Bent/3NPK 200and×(f*)
[(a*) Ecov, (b*) Ecov/3NPK, (c*) Ecov/3bent,
Ecov/6bent/3NPK].
(d*) Ecov/6bent, (e*) Ecov/3Bent/3NPK and (f*) Ecov/6bent/3NPK].
The micrographs indicate that there was a good filler/matrix interfacial interaction.
It is believed that the composites surface roughness may be associated to evaporation of
water or other substances present in inorganic components, generally associated with
their ability to interact with ambient humidity [10,40]. All samples exhibited
approximately 200-micrometer thick layers, conforming to the layer height standard (0.2
Materials 2022, 15, 6764 6 of 13

Figure 2e*,f* show a detached fillet in the micrograph, which is attributed to poor
adhesion during filament layer deposition as a result of incomplete melting and diffusion
of vicinal strands. These discontinuities and/or voids can be associated with the deposition
Materials 2022, 15,
of xthe
FORfilament
PEER REVIEW
in layers in the formation of the part. During deposition, gaps may be 7 o
partially filled (pores) due to incomplete diffusion into adjacent strands in some parts, and
slight agglomeration or saturation of the filling may be observed [22,39].
The micrographs indicate
regularity that there
and good visualwas a good
finish, filler/matrix
indicating interfacialproduced
that the filaments interaction.
are suitable
It is believed that the
use incomposites
3D [Link] roughness may be associated to evaporation of
water or other substances present in inorganic components, generally associated with their
ability to interact3.2.
withXRD Analisys
ambient humidity [10,40]. All samples exhibited approximately 200-
micrometer thick layers, XRDconforming to the layer
spectrum patterns for theheight standard
organophilic (0.2 mm)
bentonite set at20A
Cloisite printing.
®, fertilizer—N

Despite some observed

and composites with Ecovio polymer blend—are shown in Figure good
discontinuities, all samples
® showed geometric regularity and 3a. Cloisite 20
visual finish, indicating
presentsthat
two the filaments peaks,
characteristic producedone are suitable
referring fordiffraction
to 2θ use in 3D≈printing.
3.5°, associated with
(001) plane with interplanar spacing of 2.48 nm and another to a second-order p
3.2. XRD Analisys (reflection) of the (002) plane at 2θ ≈ 7.2° with a 1.23-nanometer spacing, both calcula
XRD spectrum by Bragg’s
patterns law
for(2d
thesin θ = n λ) (Figure
organophilic Cloisite 20A® , fertilizer—NPK
3a) [41,42].
bentonite
and composites withThe Ecovio ®
NPK spectrum
polymershows specificshown
blend—are peaks for inurea at 2θ
Figure = 24°,
3a. 25°, 28°,
Cloisite 20A ® 34° and
31°,
[43,44], in addition
presents two characteristic peaks, to peaks
one attributed
referring to 2θtodiffraction
ammonium≈dihydrogen ◦ phosphate
3.5 , associated withat 2θ = 16
23.7°,interplanar
the (001) plane with 29.4°, 33.8° and 38° and
spacing potassium
of 2.48 nm and dihydrogen
another tophosphate at 2θ = peak
a second-order 16.8°, 23.7°, 3
(reflection) of theand 38°plane
(002) (Figureat 3a) ≈ 7.2◦ with a 1.23-nanometer spacing, both calculated
2θ [44,45].
by Bragg’s law (2d sin θ = n λ) (Figure 3a) [41,42].

Figure 3. XRD of: Figure

(a) Cloisite 20A ® (C20A), NPK and neat Ecovio ® (Ecov); (b) XRD of: Ecov/3NPK,
3. XRD of: (a) Cloisite 20A® (C20A), NPK and neat Ecovio® (Ecov); (b) XRD of: Ecov/3N
Ecov/3Bent, Ecov/6Bent, Ecov/3Bent/3NPK
Ecov/3Bent, and Ecov/6Bent/3NPK.
Ecov/6Bent, Ecov/3Bent/3NPK and Ecov/6Bent/3NPK.

The NPK spectrum shows specific

By analyzing Figure peaks
3a, it for urea at to
is possible = 24◦ , 25
2θ observe ◦ , 28◦ , 31◦ , 34◦
that Ecovio® (Ecov) prese
◦
and 38 [43,44], characteristics
in addition toof peaks attributed to ammonium dihydrogen phosphate at amorph
both polymers that constitute it, so the graphic shows a large
2θ = 16.8◦ , 23.7◦ ,halo ◦ , 33.8◦ and 38◦ and potassium dihydrogen phosphate at 2θ = 16.8◦ ,
29.4and diffraction peaks at 16.2°, 17.4°, 20.4°, 23.1° and 24.9°. The literature reports t
23.7◦ , 33.8◦ and 38 ◦ (Figure 3a) [44,45].
the crystalline phase of the PLA presents the diffraction angles in approximately 16.2° a
By analyzing Figure 3a, it is ®
17.4°, referring topossible
the planes to observe
(110) andthat Ecovio
(203) [46,47].(Ecov) presents
However, charac-
Arruda et al. (2015) [
teristics of both polymers that constitute it, so the graphic shows a large amorphous
related the peaks in values close to those found in this study to basal reflections halo of
and diffraction peaks 16.2◦ ,(111),
planesat(010), 17.4◦ ,(100)
20.4◦and ◦ and 24.9◦ . The literature reports that the
, 23.1(111), characteristic of the PBAT crystalline phase t
crystalline phaseeventually
of the PLA presents the
overlapped the crystalline
diffractionphase anglesof in
theapproximately
PLA. Similarly,16.2 Wu,◦ and
et al. (2012) [
◦
17.4 , referring to found close values
the planes for the
(110) and crystalline
(203) [46,47]. phase of PBAT.
However, Arruda et al. (2015) [48] re-
lated the peaks in values There wasto
close anthose
increase
foundin the interplanar
in this study todistances for the nanocomposites
basal reflections of the planes contain
(010), (111), (100) bentonite
and (111), (Figure 3b), as a shift
characteristic of the
of the PBATcharacteristic
crystallinepeak of Cloisite
phase 20A® from 2θ val
that eventually
of 3.5° to close
overlapped the crystalline phase to of
2,6°theforPLA.
d001 and of the Wu,
Similarly, reflection
et al. peak
(2012)from
[49] 7.20°
foundtoclose
4.9° is observ
Interplanar
values for the crystalline phase distances
of PBAT. of nanocomposites Ecov/3Bent, Ecov/3Bent/3NPK a
There was an Ecov/6Bent/3NPK
increase in the of 1.78 nm, 1.79
interplanar nm and
distances forofthe
1.81 nm, respectively,
nanocomposites were achieved
contain-
relation to the second-order peak previously highlighted.
ing bentonite (Figure 3b), as a shift of the characteristic peak of Cloisite 20A from 2θ ®
The shift of the peaks at 3.5° and 7.20° to lower angles and the interplanar dista
increasing of the d001 plane suggest intercalation in the nanocomposites with the addit
of clay [28,41,50]. This result demonstrates the potential for delay in the release of N
fertilizer, which can be corroborated by the reduction in the release rate for syste
Materials 2022, 15, 6764 7 of 13

values of 3.5◦ to close to 2,6◦ for d001 and of the reflection peak from 7.20◦ to 4.9◦ is ob-
served. Interplanar distances of nanocomposites Ecov/3Bent, Ecov/3Bent/3NPK and
Ecov/6Bent/3NPK of 1.78 nm, 1.79 nm and of 1.81 nm, respectively, were achieved in
relation to the second-order peak previously highlighted.
The shift of the peaks at 3.5◦ and 7.20◦ to lower angles and the interplanar distance
increasing of the d001 plane suggest intercalation in the nanocomposites with the addition
of clay [28,41,50]. This result demonstrates the potential for delay in the release of NPK
fertilizer, which can be corroborated by the reduction in the release rate for systems con-
taining Cloisite 20A® bentonite, either via barrier mechanism to the diffusion of chemical
species in the matrix or by its incorporation into the structure interspersed within the clay.
Similar results were observed in the literature [51,52].
The concentration of NPK used in this study was not enough to cause phase changes
in the Ecovio® blend nor to show the diffraction peaks of the same. Only peaks be-
longing to the semi-crystalline phase of the blend, attributed to poly (butylene adipate
co-terephthalate) (PBAT), were observed in the systems Ecov/3NPK, Ecov/3Bent/3NPK
and Ecov/6Bent/3NPK.
De Lima Souza, Chiaregato and Faez (2018) [53], however, in their studies on PHB/Clay
/NPK, stated that at concentrations of 10% of NPK, the intensity of the Polyhydroxy-
butyrate (PHB) peaks decreased due to NPK dilution. The authors also identified that
the peak attributed to the basal spacing of montmorillonite at 2θ = 5◦ disappeared in
PHB/Clay/Fertilizer systems, indicating that an exfoliated structure was obtained.

3.3. Thermal Analysis

The thermal stability of the composites was analyzed by thermogravimetric mea-
surements, as shown in the TGA and Derivative Thermogravimetry (DTG) thermograms
in Figure 4.
TGA and DTG curves of the Ecovio® blend show the initial temperature (Ti) and the
final degradation temperature (Tf) for both polymers in the blend. The initial degradation
temperature of PLA and PBAT are, respectively, 300 ◦ C and 361 ◦ C, and their final degra-
dation temperatures are 361 ◦ C and 450 ◦ C. Peaks at approximately 360 ◦ C refer to the
decomposition of PLA, and the second event with a peak at approximately 401 ◦ C refers to
the thermal degradation of PBAT. The two distinct events can be attributed to poor thermo-
dynamic compatibility between the two polymers, as reported in the literature [27,54–56].
The data show that PBAT has greater thermal stability than PLA. This is due to the fact
that PBAT has a benzene ring in its molecular structure, which suppresses the movement
of the polymer chain, resulting in higher thermal stability [57]. Degradation of PLA takes
place by main chain scission and the formation of products such as cyclic oligomer, lactide
and carbon monoxide [58].
The Ecov/3Bent system shows a shift to a lower degradation temperature in the PLA
region. Similar behavior was reported by Taleb et al. (2021) [59] on PLA nanocomposites
reinforced with modified nanoclays. The authors related the accelerated decomposition
involving the clay for compositions of up to 3% to the hydrolysis reaction arising from
small fractions of water or impurities that may exist in the montmorillonite, catalyzed
by hydroxyl groups. As described by Alves et al. (2020) [60], who related degradation
behaviors for PLA nanocomposites with different types of clays, including Cloisite 20A® ,
there is a relationship between the organic and inorganic portions through the hydrolysis
generated by the fractions of water and impurities found in clay mineral, generating a
catalytic effect and/or aminolysis associated with the ammonium surfactant. However,
Tan, He and Qu (2019) [61] showed different results in their study with PLA/PBS/OMMT
nanocomposites. The authors demonstrated that with uniformly dispersed, intercalated
and exfoliated clay, in compositions of up to 5% clay, the thermal stability increased.
This result was attributed to the good dispersion of clay in the matrix. In this study, in
compositions above 5%, there was a decrease in thermal stability, which, according to the
 obtained.

3.3. Thermal Analysis

The thermal stability of the composites was analyzed by thermogravimetric
measurements, as shown in the TGA and Derivative Thermogravimetry (DTG)
Materials 2022, 15, 6764 thermograms in Figure 4. 8 of 13
TGA and DTG curves of the Ecovio blend show the initial temperature (Ti) and the
®

final degradation temperature (Tf) for both polymers in the blend. The initial degradation
temperature
authors, isofdue
PLA and PBAT
to excess are,from
oxygen respectively, 300 °C
the hydroxyl and of
group 361
the°C, and theirinfinal
surfactant the clay or
degradation temperatures are 361 °C and 450 °C. Peaks
poor dispersion, which was not observed in their work. at approximately 360 °C refer to
the decomposition of PLA, and the second event with a peak at approximately 401 °C
In our work, no significant variation in the thermal stability of the blend was observed for
refers to the thermal degradation of PBAT. The two distinct events can be attributed to
the other clay and/or fertilizer compositions (Ecov/3NPK, Ecov/6Bent, Ecov/3Bent/3NPK,
poor thermodynamic compatibility between the two polymers, as reported in the litera-
Ecov/6Bent/3NPK), showing that there was no expressive variation in thermal stability
ture [27,54–56].
compared to pure Ecovio® .

Materials 2022, 15, x FOR PEER REVIEW 9 of 15

Figure 4. TGA of the systems: Ecov; Ecov/3NPK; Ecov/3Bent; Ecov/6Bent; Ecov/3Bent/3NPK;

Figure 4. TGA of the systems: Ecov; Ecov/3NPK; Ecov/3Bent; Ecov/6Bent; Ecov/3Bent/3NPK;
Ecov/6Bent/3NPK.
Ecov/6Bent/3NPK.
3.4. NPK Release
The data show that PBAT has greater thermal stability than PLA. This is due to the
The average percentages of active compounds released by the filaments are shown
fact that PBAT has a benzene ring in its molecular structure, which suppresses the
in Figure 5. All systems exhibited considerable attenuation in the release of active com-
movement of the polymer chain, resulting in higher thermal stability [57]. Degradation of
pounds compared to free NPK. In up to 24 h of testing, the systems average cumulative
PLA takes place by main chain scission and the formation of products such as cyclic
release rate of NPK was, respectively, 21.00% and 19.67% for Ecov/3Bent/3NPK and
oligomer, lactide and carbon monoxide [58].
Ecov/6Bent/3NPK. In this initial period, systems containing bentonite released about 22%
The Ecov/3Bent system shows a shift to a lower degradation temperature in the PLA
less fertilizer
region. than thewas
Similar behavior Ecov/3NPK
reported bysystem.
Taleb etThis difference
al. (2021) [59] onis PLA
probably due to the higher
nanocomposites
concentration of nanoparticles that generate more barriers to the diffusion
reinforced with modified nanoclays. The authors related the accelerated decomposition of NPK chemical
species [62,63]. The Ecov/6Bent/3NPK system showed the greatest potential
involving the clay for compositions of up to 3% to the hydrolysis reaction arising from for release
control with an average cumulative release rate of 81.85% after 120 h, while
small fractions of water or impurities that may exist in the montmorillonite, catalyzed by in the same
period,groups.
hydroxyl the Ecov/3NPK system
As described byreleased
Alves et100% of the [60],
al. (2020) [Link] related degradation
behaviors for PLA nanocomposites with different types of clays, including Cloisite 20A®,
there is a relationship between the organic and inorganic portions through the hydrolysis
generated by the fractions of water and impurities found in clay mineral, generating a
catalytic effect and/or aminolysis associated with the ammonium surfactant. However,
Tan, He and Qu (2019) [61] showed different results in their study with PLA/PBS/OMMT
 cumulative release rate of NPK was, respectively, 21.00% and 19.67% for
Ecov/3Bent/3NPK and Ecov/6Bent/3NPK. In this initial period, systems containing
cumulative
bentonite release
released aboutrate
22%oflessNPK was, than
fertilizer respectively, 21.00%system.
the Ecov/3NPK and This
19.67% for
difference is
Ecov/3Bent/3NPK
probably due to the and Ecov/6Bent/3NPK.
higher concentration ofInnanoparticles
this initial period, systems more
that generate containing
barriers to
thebentonite
diffusionreleased
of NPK about 22% less
chemical fertilizer
species than the
[62,63]. TheEcov/3NPK system. This
Ecov/6Bent/3NPK difference
system is the
showed
Materials 2022, 15, 6764 probably due to the higher concentration of nanoparticles that generate more barriers to 9 of 13
greatest potential for release control with an average cumulative release rate of 81.85%
the diffusion of NPK chemical species [62,63]. The Ecov/6Bent/3NPK system showed the
after 120 h, while in the same period, the Ecov/3NPK system released 100% of the NPK.
greatest potential for release control with an average cumulative release rate of 81.85%
after 120 h, while in the same period, the Ecov/3NPK system released 100% of the NPK.

Figure
Figure 5. AverageNPK
5. Average
Average NPKrelease
release percentage.
percentage.
Figure 5. NPK release percentage.

[Link].
3.5. Release
Release
Release Kinetics
Kinetics
Kinetics
Figure 6 shows the NPK release profiles using different mathematical models
Figure
Figure6 6showsshows the the
NPKNPK release profiles
release using different
profiles mathematical
using different models described
mathematical models
described in the literature [64]. The data show that the release curves fitted better to the
in the literature
described [64]. The data show that theshow
release curves fitted better to the semi-empirical
semi-empirical models of Higuchi and Korsmeyer-Peppas due the highest correlation to the
in the literature [64]. The data that the release curves fitted better
models of Higuchi
semi-empirical
coefficient (R²)modelsandThe
values. Korsmeyer-Peppas
of Higuchi due thethehighest
and Korsmeyer-Peppas
Higuchi model describes correlation
release due
of thethe coefficient
highest
active (R2 )
correlation
compound
values. The(R²)
coefficient
homogeneouslyHiguchi
[Link]
The describes
dispersed Higuchi
in thematrix,
model
a uniform release of thethe
describes
which active compound
release
behaves as aofdiffusionhomogeneously
the active compound
medium
dispersed
homogeneously
[65,66]. in a uniform matrix, which behaves as a diffusion medium [65,66].
dispersed in a uniform matrix, which behaves as a diffusion medium
[65,66].

Materials 2022, 15, x FOR PEER REVIEW 11 of 15

(a) (b)

(a) (b)

(c) (d)
Figure 6. Data fitting to (a) zero-order; (b) first-order; (c) Higuchi; (d) Korsmeyer-Peppas kinetic
Figure 6. Data fitting to (a) zero-order; (b) first-order; (c) Higuchi; (d) Korsmeyer-Peppas kinetic
models for NPK release by the different composites investigated.
models for NPK release by the different composites investigated.
The correlation coefficients for the Korsmeyer-Peppas model were
0.8998(Ecov/3NPK), 0.8386(Ecov/3Bent/3NPK) and 0.7853(Ecov/6Bent/3NPK). This model
is used when there is a possibility that more than one release mechanism is involved and
the characterization of the release kinetics is performed based on the value of n (release
exponent) [35,36,44]. This range of n values, between 0.5 and 1.0, characterizes non-
Materials 2022, 15, 6764 10 of 13

The correlation coefficients for the Korsmeyer-Peppas model were 0.8998(Ecov/3NPK),

0.8386(Ecov/3Bent/3NPK) and 0.7853(Ecov/6Bent/3NPK). This model is used when there
is a possibility that more than one release mechanism is involved and the characterization of
the release kinetics is performed based on the value of n (release exponent) [35,36,44]. This
range of n values, between 0.5 and 1.0, characterizes non-Fickian anomalous transport. In
this case, the release kinetics are conducted by swelling and diffusive phenomena [67]. The
sorption and transport of molecules are directly affected by the existence of microcavities
present in the matrix and the diffusion and relaxation rates of the polymer chains are
similar [68,69].
As previously shown in in Figure 5, the release profile of NPK from all the samples
exhibited a pronounced initial release phase until 48 h of immersion time. This profile
is probably due to burst release of fertilizer available in systems surface, which occurs
immediately (because of NPK inorganic salts instantaneous dissolution in water), followed
by a subsequent release governed by diffusive phenomena [34]. For Ecov/3NPK, a value
of n = 0.52 and fast kinetics were observed compared to systems with organobentonite
(Figure 6d). This value close to 0.5 indicates that kinetics of this system were mostly driven
by diffusive phenomena. For Ecov/3Bent/3NPK and Ecov/6Bent/3NPK, after 48 h, the
slope of the curves changed and exhibited a remarkable slower release rate. The release
exponents for these systems were, respectively, n = 0.68 e n = 0.58, indicating that the
kinetics were probably governed by diffusion and swelling phenomena associated with the
barrier effect generated by organobentonite [34,70,71].

4. Conclusions
In this study, we produce filaments of PLA/PBAT and NPK fertilizer adsorbed on
organophilized bentonite intended for application in the prototyping of biodegradable
agricultural artifacts in 3D printing using the FDM technique. The nanocomposite filaments
produced have diameter ranges suitable for application in commercial 3D printers. Optimal
parameters were defined for printing the filaments, which resulted in pieces with dimen-
sional regularity. Scanning electron microscopy showed that a good surface quality of the
printed specimens was achieved. Thermogravimetric analysis showed that the thermal
stability of the matrix was not significantly altered by nanofiller and/or fertilizer incorpo-
ration. Organoclay addition was effective in increasing fertilizer release period. Especially,
Ecov/6Bent/3NPK has the greatest potential for release control with an average cumulative
release rate of 81.85% after 120 h. Finally, the filaments produced have the potential for
slow or controlled release of fertilizer and are very promising to be applied in FDM in
innovative planting techniques that can reduce the release of active compounds into the
environment and mitigate environmental impacts. For future studies, the comparison of
different types of organobentonite can be considered in order to evaluate the influence of
surfactant (ionic and nonionic) on the adsorption of chemical species from fertilizers and
on release performance. A continuous process based on a twin-screw extruder can also be
considered in order to simplify filament production, and future research will be pursued to
determine the ecotoxicity of nanocomposites.

Author Contributions: T.C.P.d.S. and T.S.A. generated the idea and led the writing. A.G.d.S.F. and
I.R.d.A. delivered in the production of samples. R.B. and Y.M.B.d.A. managed data production.
T.C.P.d.S., A.G.d.S.F. and I.R.d.A. edited the manuscript. T.S.A., R.B. and L.H.d.C. reviewed and
edited the manuscript. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Acknowledgments: The authors are grateful for the technical support of the Federal University of
Campina Grande and the Federal University of Pernambuco.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2022, 15, 6764 11 of 13

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