materials

Article
Bio-Composite Filaments Based on Poly(Lactic Acid) and Cocoa
Bean Shell Waste for Fused Filament Fabrication (FFF):
Production, Characterization and 3D Printing
Daniela Fico 1,2 , Daniela Rizzo 3, * , Valentina De Carolis 1 and Carola Esposito Corcione 1

1 Department of Engineering for Innovation, University of Salento, Edificio P, Campus Ecotekne,

s.p. 6 Lecce-Monteroni, 73100 Lecce, Italy; [email protected] (D.F.);
[email protected] (V.D.C.); [email protected] (C.E.C.)
2 Italian National Council of Research-Institute of Heritage Sciences (CNR-ISPC), Campus Ecotekne,
73100 Lecce, Italy
3 Department of Cultural Heritage, University of Salento, Via D. Birago 64, 73100 Lecce, Italy
* Correspondence: [email protected]

Abstract: In this study, novel biocomposite filaments incorporating cocoa bean shell waste (CBSW)
and poly(lactic acid) (PLA) were formulated for application in Fused Filament Fabrication (FFF)
technology. CBSW, obtained from discarded chocolate processing remnants, was blended with PLA
at concentrations of 5 and 10 wt.% to address the challenge of waste material disposal while offering
eco-friendly composite biofilaments for FFF, thereby promoting resource conservation and supporting
circular economy initiatives. A comprehensive analysis encompassing structural, morphological,
thermal, and mechanical assessments of both raw materials and resultant products (filaments and
3D printed bars) was conducted. The findings reveal the presence of filler aggregates only in high
concentrations of CBSW. However, no significant morphological or thermal changes were observed
at either CBSW concentration (5 wt.% and 10 wt.%) and satisfactory printability was achieved. In
addition, tensile tests on the 3D printed objects showed improved stiffness and load resistance in these
samples at the highest CBSW concentrations. In addition, to demonstrate their practical application,
Citation: Fico, D.; Rizzo, D.; De several 3D prototypes (chocolate-shaped objects) were printed for presentation in the company’s
Carolis, V.; Esposito Corcione, C. shop window as a chocolate alternative; while retaining the sensory properties of the original cocoa,
Bio-Composite Filaments Based on the mechanical properties were improved compared to the base raw material. Future research will
Poly(Lactic Acid) and Cocoa Bean focus on evaluating indicators relevant to the preservation of the biocomposite’s sensory properties
Shell Waste for Fused Filament and longevity.
Fabrication (FFF): Production,
Characterization and 3D Printing.
Keywords: waste; cocoa shell; 3D printing; fused filament fabrication; PLA; circular economy
Materials 2024, 17, 1260. https://
doi.org/10.3390/ma17061260

Academic Editor: Young-Hag Koh

1. Introduction
Received: 31 January 2024
Revised: 28 February 2024 Respect for the environment and sustainability are issues of great concern today due to
Accepted: 6 March 2024 the growing problem of the disposal of industrial production waste. The circular economy
Published: 8 March 2024 (CE), a sustainable system that aims to reduce the consumption of raw materials and the
production of waste by reintegrating them into a closed production cycle, underpins this
research effort [1,2]. Disposal poses a significant challenge in the food industry, exacerbated
by factors such as population growth. In particular, the escalating global demand for
Copyright: © 2024 by the authors.
chocolate, a popular foodstuff in confectionery around the world, has led to a dramatic
Licensee MDPI, Basel, Switzerland.
increase in the production of cocoa bean shell waste (CBSW) [3]. CBSW (100% cocoa bean
This article is an open access article
shell) is typically repurposed as organic fertilizer, animal feed, or fuel, albeit with adverse
distributed under the terms and
environmental consequences [4]. In very few studies, CBSW is used as a renewable resource
conditions of the Creative Commons
and as an additive to polymer matrix such as poly(lactic acid), PLA, which is known for
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
its versatility and suitability in 3D printing with FFF technology [5,6]. Among the various
4.0/).
methods for recycling waste materials, additive manufacturing (AM), or 3D printing, which

Materials 2024, 17, 1260. https://doi.org/10.3390/ma17061260 https://www.mdpi.com/journal/materials

Materials 2024, 17, 1260 2 of 14

facilitates the production of complex prototypes from computer-aided design (CAD) models
while minimizing material waste [7,8], may be one of the most promising techniques. Its
versatility extends to various industries, including advanced medicine and food processing,
aligning with the transition from a linear to a circular economy model [9–11]. Previous
research has demonstrated AM’s potential to reduce waste production, enhance product
value, and promote sustainability [12–14]. Studies by Sanyang et al. [15], Papadopoulou
et al. [16], and Tran et al. [17] have explored the use of cocoa waste in composite films
and biocomposites, showcasing its potential as a natural filler with ecological benefits.
Additionally, Leonard and Berrio [18] investigated PLA-based filaments incorporating
cocoa husk for biomedical applications, noting improvements in compressive strength
without altering thermal properties [19,20]. Andres J. Garcia-Brand et al. [21] pioneered
a method for utilizing CBSW as reinforcement to enhance the bioactivity of synthetic
polymeric materials in biomedical research. TGA and DSC thermograms unveiled the
feasibility of employing various processing techniques, such as compression molding,
extrusion, and potentially 3D printing. However, they did not explore the utilization of any
3D printing technology for fabricating 3D models using composite materials. In this study,
biofilaments comprising PLA and CBSW at varying concentrations were developed and
used to produce 3D models by FFF, offering a novel approach to waste recycling and reuse
through FFF printing. The findings highlight the feasibility of integrating waste materials
into the production cycle while emphasizing the importance of sustainable practices in
modern manufacturing [22–25]. Based on this scenario, the aim of this study was to develop
and characterize biocomposite filaments made from poly(lactic acid) and 5–10 wt.% of cocoa
bean shell waste for FFF printing technology, from a CE perspective. The developed green
filaments were subjected to morphological–structural, thermal and mechanical analyses.
For the first time, the authors tested the feasibility of the FFF printing process to produce
new 3D objects from waste materials, with the aim of permitting their integration into
the same material production cycle (company-to-company). The work highlights the
importance of sustainable practices in modern manufacturing while using solvent-free,
inexpensive and easy-to-use methods.

2. Materials and Methods

The technical specifications of the materials utilized for the creation of composite
biofilaments, manufacturing methodologies, and analytical techniques for structural, mor-
phological, thermal, and mechanical characterization are outlined as follows.

2.1. Materials
The Ingeo 4043D poly(lactic acid) (NatureWorks LLC, Blair, NE, USA) employed as
the polymer matrix for fabricating the composite filaments was obtained in pellet form.
It possesses a density of 1.24 g cm−3 and a melt flow index (MFI) of 6 g/10 min at a
temperature of 210 ◦ C. PLA was utilized both independently to produce a virgin filament
(100PLA) and as a polymer matrix for creating two biofilaments incorporating CBSW as
fillers at 5 wt.% and 10 wt.%, respectively. Initially, the PLA pellets, with a diameter of
approximately 5 mm (manufacturer’s data sheet), were stored in an oven at 60 ◦ C for 24 h
before being reduced into particles using the Retsch ZM 100 Ultracentrifugal mill (Retsch
GmbH, Haan, Germany) equipped with a sieve with a mesh diameter of 0.75 mm.
The cocoa bean shell waste (CBSW) utilized in the production of the new compos-
ite filaments originates from the manufacturing residues of the company “Maglio Arte
Dolciaria S.R.L.” (Maglie, Lecce, Apulia, Italy). Supplied by the company in the form of
coarse-grained and heterogeneous powder, it exhibits the characteristic brown color of
cocoa and a robust chocolate-like odor. Prior to utilization, the CBSW was subjected to
storage in an oven at 60 ◦ C for 24 h and subsequently reduced into particles using the
Retsch ZM 100 Ultracentrifugal mill (Retsch GmbH, Haan, Germany) equipped with a
sieve with a mesh diameter of 0.25 mm.
 Materials 2024, 14, x FOR PEER REVIEW 3 of 14

Materials 2024, 17, 1260 3 of 14

Retsch ZM 100 Ultracentrifugal mill (Retsch GmbH, Haan, Germany) equipped with a
sieve with a mesh diameter of 0.25 mm.

2.2.
2.2.Production
ProductionofofBiofilaments
Biofilamentsfor
forFFF
FFF
The
The PLA and CBSW powders were
PLA and CBSW powders were initially
initially combined manually at
combined manually at room
room temperature
temperature
before being introduced into the extrusion chamber of the 3Devo Composer 450
before being introduced into the extrusion chamber of the 3Devo Composer 450 Filament Filament
Maker single-screw extruder (Utrecht, The Netherlands,), as reported in Figure
Maker single-screw extruder (Utrecht, The Netherlands,), as reported in Figure 1. 1.

Figure1.1. 3Devo
Figure 3Devo Composer
Composer 450
450 Filament
Filament Maker
Makersingle-screw
single-screwextruder
extruderwith
withindication
indicationofofdifferent
different
temperature zones.
temperature zones.

Theparameters
The parametersused
usedtotoproduce
producethe
thefilaments
filamentsbybythe
the extrusion
extrusion process
process areare outlined
outlined in
Table 1, while the labels and compositions of the materials used and developed are listedare
in Table 1, while the labels and compositions of the materials used and developed in
listed2.in Table 2.
Table

Table1.1.Extrusion
Table Extrusionprocess
processparameters
parametersfor
forfilaments.
filaments.

Extrusion
Extrusion Process
Process Parameters
Parameters 100PLA
100PLA 95PLA/5CBSW
95PLA/5CBSW 90PLA/10CBSW
90PLA/10CBSW
Screw speed(rpm)
Screw speed (rpm) 3.53.5 44 44
Fan
Fan cooling speed(%)
cooling speed (%) 0 0 3030 30
30
Feed zone
Feed temperature(◦ (°C)
zone temperature C) 170170 165
165 165
165
Compression zone temperature
Compression zone temperature (◦ C)
(°C) 185185 180
180 180
180
Metering zone temperature (◦ C) 190 185 185
Metering zone temperature
◦
Die temperature ( C)
(°C) 200
190 185
165
185
165
Die temperature (°C) 200 165 165

Table2.2.Raw
Table RawMaterials,
Materials,biofilament
biofilamentand
and3D
3Dprinted
printedsample
sample labels
labels and
and weight
weight composition
composition (wt.%).
(wt.%).

Label
Label TypeType Composition
Composition (wt.%)
(wt.%)
PLA
PLA RawRawmaterial 100 PLA
material 100Ingeo 4043D
PLA Ingeo pellet
4043D pellet
CBSW
CBSW RawRawmaterial 100 Cocoa
material bean bean
100 Cocoa shellshell
waste powder
waste powder
100PLA
100PLA Filament
Filament 100 PLA Ingeo
100 PLA Ingeo 4043D 4043D
95PLA/5CBSW Filament 95 PLA Ingeo 4043D and 5 Cocoa bean shell waste
95PLA/5CBSW Filament 95 PLA Ingeo 4043D and 5 Cocoa bean shell waste
90PLA/10CBSW Filament 90 PLA Ingeo 4043D and 10 Cocoa bean shell waste
90PLA/10CBSW
100PLA_3D Filament
3D sample 90 PLA Ingeo
100 PLA 4043D and 10 Cocoa bean shell waste
Ingeo 4043D
100PLA_3D
95PLA/5CBSW_3D 3D sample 3D sample 100 PLA Ingeo
95 PLA 4043D
Ingeo 4043D and 5 Cocoa bean shell waste
90PLA/10CBSW_3D 3D sample
95PLA/5CBSW_3D 3D sample 95 PLA 90Ingeo
PLA Ingeo
4043D4043D
and and 10 Cocoa
5 Cocoa beanbean shell
shell waste
waste
90PLA/10CBSW_3D3D sample 90 PLA Ingeo 4043D and 10 Cocoa bean shell waste
2.3. 3D Printing
2.3. 3D Printing
Three-dimensional samples were printed on the Creality CP-01 printer (Creality, Lon-
don, UK) in accordance with the European standard used for the tensile tests
ISO 527-2(2012) [26]. The following printing parameters were used: extrusion temper-
ature 200 ◦ C, plate temperature 50 ◦ C, print speed 50 mm/s, fill 100% and fan speed 100%.
Materials 2024, 17, 1260 4 of 14

The CAD model was developed using Fusion 360 software (Autodesk, San Rafael, CA,
USA) and converted to a G-code file using Cura software, Ultimaker Cura version 5.1.1.
(Ul-timaker B.V., Utrecht, The Netherlands). Finally, after studying the structural, thermal
and mechanical properties of the biocomposites, some design objects (some traditional
chocolate shapes) were printed for display in the window of the company that supplied
the cocoa waste. The CAD models were developed using Fusion 360 software (Autodesk,
San Rafael, CA, USA) and converted to Gcode files using Cura software, (Ultimaker B.V.,
Utrecht, The Netherlands). Prints were made with the Creality CP-01 printer (Creality,
London, UK) with the following operating parameters: extrusion temperature 190 ◦ C, plate
temperature 50 ◦ C, print speed 60 mm/s and infill 20%.
Three-dimensional objects (chocolate shaped objects) were also printed to demonstrate
the printability of complex shapes with the recycled filaments. For this purpose, the
BQ Hephestos 2 printer (BQ, Barcelona, España) was used with the following printing
parameters: extrusion temperature 200 ◦ C, plate temperature 0 ◦ C, printing speed 60 mm/s
and infill 20%.
A comprehensive list of all materials employed in this study is provided in Table 2.

2.4. Methods
The morphological characterization of the raw materials and the biofilaments pro-
duced was carried out using a scanning electron microscope (SEM), model Zeiss E Evo 40
(Oberkochen, Germany).
Fourier transform infrared spectroscopy (FTIR) analyses were performed on the raw
materials (PLA and CBSW powders) to perform a preliminary chemical structural character-
ization. FTIR spectra were obtained on KBr pellets using a JASCO FT/IR 6300 spectrometer
(Easton, MD) with a resolution of 4 cm−1 , setting up 64 scans in the region between
4000 and 600 cm−1 . Five spectra were considered for each replicate sample.
XRD measurements of the raw materials and biofilaments were performed with a
Rigaku Ultima + diffractometer (Tokyo, Japan) using CuKα radiation (λ = 1.5418 Å) in the
step scan mode, recorded in the 2θ range from 2–60◦ , with a step size of 0.02◦ and a step
duration of 0.5 s. Five spectra were considered for each replicate sample.
DSC analysis (Mettler Toledo DSC1 StareSystem) was performed on raw materials,
filaments and 3D printed rods to investigate thermal properties by measuring the glass
transition temperature (Tg ), crystallization temperature (Tc ) and melting temperature (Tm ).
The analyses were performed over a temperature range of 25 ◦ C to 200 ◦ C at a heating rate
of 10 ◦ C/min.
According to the ISO 527-2(2012) standard [26], tensile tests were performed on the 3D
printed sample using a Lloyd LR5K dynamometer (Lloyd Instruments Ltd., Bognor Regis,
UK) at a strain rate of 1 mm/min. The grips used in these tests were wedge-type grips,
the distance between grips was 58 mm, and the load cell was 5 kN. The dimensions of the
specimen refer to the 1BA type, according to the standard. Five replicates were performed
for each specimen.
Magnified images of the sections of the 3D printed tensile samples were obtained us-
ing the Dino Lite digital microscope instrument (AnMo Electronics Corporation, New Taipei
City, Taiwan) to understand the morphology and adhesion of the different
deposited layers.

3. Results and Discussion

3.1. Characterization of Raw Materials
The morphological–structural, chemical and thermal features of all raw materials used
to produce biofilaments were investigated. The results of the SEM, FTIR, XRD and DSC
analyses of the raw materials are shown below.
After the milling process, SEM images (Figure 2A,B) at high magnifications (100×
and 1000×) of the neat PLA particles show an irregular, square shape and a diameter
up to about 500 µm. The cocoa bean shell waste (CBSW) was supplied in the form of a
 3.1. Characterization of Raw Materials
The morphological–structural, chemical and thermal features of all raw materials
used to produce biofilaments were investigated. The results of the SEM, FTIR, XRD and
DSC analyses of the raw materials are shown below.
Materials 2024, 17, 1260 After the milling process, SEM images (Figure 2A,B) at high magnifications (100 5 of X
14
and 1000 X) of the neat PLA particles show an irregular, square shape and a diameter up
to about 500 µm. The cocoa bean shell waste (CBSW) was supplied in the form of a coarse-
grained, inconstant
coarse-grained, powder,powder,
inconstant after grinding the cocoa
after grinding thebean
cocoashell.
beanFurthermore, as visible
shell. Furthermore, as
from the SEM image (Figure 2C,D), the CBSW particle size varies from about
visible from the SEM image (Figure 2C,D), the CBSW particle size varies from about 5 µm to
5 µm
about 200200
to about µm.µm.

Figure 2. SEM images of raw materials: (A) PLA pellet magnification 100× and (B) magnification
Figure 2. SEM images of raw materials: (A) PLA pellet magnification 100 X and (B) magnification 1
1K×; (C) cocoa bean shell waste magnification 100× and (D) magnification 1K×.
KX; (C) cocoa bean shell waste magnification 100 X and (D) magnification 1 KX.
Materials 2024, 14, x FOR PEER REVIEW 6 of 14
The chemical characterization of the raw materials was carried out using FTIR spec-
The chemical characterization of the raw materials was carried out using FTIR
troscopy. The infrared spectra of PLA powder and CBSW are shown in Figure 3.
spectroscopy. The infrared spectra of PLA powder and CBSW are shown in Figure 3.
The infrared spectrum of the PLA shows asymmetrical and symmetrical –CH3 and –
CH3 stretching frequencies at 2995 cm−1 and 2946 cm−1, respectively, and a characteristic
peak of C=O stretching at about 1746 cm−1 [27]. The peaks at 1452 cm−1 and 1365 cm−1 are
associated with the asymmetric and symmetric bending vibrations of the –CH3 groups,
respectively, while the band at about 1084 cm−1 corresponds to the C–O bond [27].
In the FTIR spectrum of the CBSW, the band present at around 3300 cm−1 is associated
with OH groups, while the peaks at 2932 cm−1 and 2870 cm−1 correspond to the asymmetric
and symmetric stretching vibrations of the C–H groups of cellulose and hemicellulose.
The infrared peak at 1741 cm−1 corresponds to the C=O stretching of saturated esters, while
the three infrared bands at approximately 1638 cm−1, 1521 cm−1 and 1401 cm−1 correspond
to amide I, II and III, respectively. These bands can be associated with proteins, lignin and
polysaccharides present in the biomass. Finally, the peaks at 1240 cm−1 and 1023 cm−1 are
associated with holocellulose biomolecules [28].

FigureFigure FTIR spectra

3. FTIR3.spectra of PLAofpellet
PLA pellet and cocoa
and cocoa beanwaste
bean shell shell waste and infrared
and main main infrared
peaks.peaks.

In the XRD diffractogram of the PLA (Figure 4A), more defined diffraction peaks
emerge at 2θ = 16.70° and at 2θ = 19.10° over a broad amorphous band, assigned to the
crystalline plane (110) and (203), respectively [14]. The diffractogram of the CBSW sample
(Figure 4A) shows peaks at 2θ = 3.09°, 19.5°, 21.20°, 22.02° (002), 23.11° and 24.30°, some
Materials 2024, 17, 1260 6 of 14

The infrared spectrum of the PLA shows asymmetrical and symmetrical –CH3 and
–CH3 stretching frequencies at 2995 cm−1 and 2946 cm−1 , respectively, and a characteristic
peak of C=O stretching at about 1746 cm−1 [27]. The peaks at 1452 cm−1 and 1365 cm−1
are associated with the asymmetric and symmetric bending vibrations of the –CH3 groups,
respectively, while the band at about 1084 cm−1 corresponds to the C–O bond [27].
In the FTIR spectrum of the CBSW, the band present at around 3300 cm−1 is associated
with OH groups, while the peaks at 2932 cm−1 and 2870 cm−1 correspond to the asymmetric
and symmetric stretching vibrations of the C–H groups of cellulose and hemicellulose. The
infrared peak at 1741 cm−1 corresponds to the C=O stretching of saturated esters, while the
three infrared bands at approximately 1638 cm−1 , 1521 cm−1 and 1401 cm−1 correspond to
amide I, II and III, respectively. These bands can be associated with proteins, lignin and
polysaccharides present in the biomass. Finally, the peaks at 1240 cm−1 and 1023 cm−1 are
associated with holocellulose biomolecules [28].
In the XRD diffractogram of the PLA (Figure 4A), more defined diffraction peaks
emerge at 2θ = 16.70◦ and at 2θ = 19.10◦ over a broad amorphous band, assigned to the
crystalline plane (110) and (203), respectively [14]. The diffractogram of the CBSW sample
(Figure 4A) shows peaks at 2θ = 3.09◦ , 19.5◦ , 21.20◦ , 22.02◦ (002), 23.11◦ and 24.30◦ , some of
which are characteristic of crystalline polymorphs of cellulose [29,30]. The cocoa bean from
which the powder was obtained is composed of about 60 wt.% water and holocellulose
Materials 2024, 14, x FOR PEER REVIEW 7 of 14
(cellulose, hemicellulose, pectin) and then lignin [29] and its XRD diffractogram is very
similar to cocoa butter [31].

Figure (A)
4. 4.
Figure XRD
(A) diffractograms
XRD and
diffractograms (B)(B)
and DSC curve
DSC of of
curve raw materials.
raw materials.

3.2.ACharacterization
DSC analysis was performed on raw materials to investigate thermal properties
of Biofilaments
(Figure 4B). In the DSC curve of poly(lactic acid), the glass transition temperature (Tg ) was
SEM analyses were performed on the external surfaces of the composite filaments to
measured using the inflection point method with the STARe System version 11 software
investigate surface roughness and on the cross-section of filaments◦to verify homogeneity
(Mettler Toledo, Milan, Italy) [12] and corresponds for PLA to 61.72 C. In Figure 4B, it is
(Figure
also observed5). The
thatsurface
the Tg isofaccompanied
the composite byfilament becomespeak
an endothermic slightly irregular
(relaxation after the
enthalpy)
addition of CBSW (Figure 5D–F), and some discontinuity areas are
due to the transformation of the polymer from the glassy to the liquid-viscous or rubbery observed (Sample
95PLA/5CBSW).
state [32]. The DSC This phenomenon
curve also showsbecomes
a melting more
peak pronounced
at temperaturewith Ttheof increase
149.37 inandthe
m
amount of filler added to the polymer matrix (Sample 90PLA/10CBSW),
melting enthalpy ∆Hm of 19.90 J/g. In the present investigation, the DSC curves of CBSW where the surface
appearswere
samples completely rough (Figure
also examined. As with 5G–I).
PLA,Furthermore,
the average as shown
values by the from
obtained cross-sectional
the five
images of the two produced FFF biofilaments, the cocoa particles
measurements are shown in Figure 4B. The DSC analysis was carried out in the aggregate in maximum
some places
and these aggregates
temperature are even used
range commonly more in visible
FFF in the filament
printing containing
with PLA 10 wt.%
filaments, i.e., CBSW.
betweenThe
25phenomenon
and 200 C. appears
◦ CBSW istoabe attributable
complex not only
biomass to a different
consisting diameter
of several of the particles
components, such asin
the mixture
proteins, lignin(PLA approximately 500
and polysaccharides, µm measured
as previously by SEM
reported. and CBSW
Moreover, 5 µm
similar to 1 mm
to woody
diameter measured by SEM), but also to a different chemical nature
biomass, the main polysaccharide components, consisting of hemicellulose, cellulose and that creates poor
interfacial adhesion. This occurrence is already known in the literature
lignin, manifest maximum endothermal peaks in different ranges according to the scientific for various PLA-
based composites
literature and waste
[33,34]. Therefore, it can fillers with different
be concluded polarities
that the double and maypeak
endothermic indicate the
present
possibility in the future of using plasticizer agents that improve the compatibility and
adhesiveness of the different substances [35].
Materials 2024, 17, 1260 7 of 14

in the CBSW-DSC curve only refers to the thermal decomposition of hemicellulose and
partially of cellulose.

3.2. Characterization of Biofilaments

SEM analyses were performed on the external surfaces of the composite filaments to
investigate surface roughness and on the cross-section of filaments to verify homogeneity
(Figure 5). The surface of the composite filament becomes slightly irregular after the
addition of CBSW (Figure 5D–F), and some discontinuity areas are observed (Sample
95PLA/5CBSW). This phenomenon becomes more pronounced with the increase in the
amount of filler added to the polymer matrix (Sample 90PLA/10CBSW), where the surface
appears completely rough (Figure 5G–I). Furthermore, as shown by the cross-sectional
images of the two produced FFF biofilaments, the cocoa particles aggregate in some places
and these aggregates are even more visible in the filament containing 10 wt.% CBSW. The
phenomenon appears to be attributable not only to a different diameter of the particles
in the mixture (PLA approximately 500 µm measured by SEM and CBSW 5 µm to 1 mm
diameter measured by SEM), but also to a different chemical nature that creates poor
interfacial adhesion. This occurrence is already known in the literature for various PLA-
based composites and waste fillers with different polarities and may indicate the possibility
Materials 2024, 14, x FOR PEER REVIEW 8 of 14
in the future of using plasticizer agents that improve the compatibility and adhesiveness of
the different substances [35].

Figure 5.
Figure 5. SEM
SEM images
imagesofoffilaments:
filaments:(A)(A)100PLA
100PLAexternal filament
external filamentsurface magnification
surface 1.0 1.0K
magnification ×,
KX, (B)
section
(B) magnification
section 100100
magnification X (C) section
× (C) magnification
section 500500
magnification X; ×(D) 95PLA/5CSBW
; (D) 95PLA/5CSBW external filament
external fila-
surface
ment magnification
surface 1.0 KX,
magnification (E)
1.0K ×,section magnification
(E) section 100 X,
magnification 100(F)
×,section magnification
(F) section 1.0 KX;
magnification 1.0K(G)
×;
90PLA/10CSBW external filament surface magnification 1.0 KX, (H) section magnification
(G) 90PLA/10CSBW external filament surface magnification 1.0K×, (H) section magnification 100 100 X, ×
(I),
section magnification 1.0 KX.
(I) section magnification 1.0K×.

XRDspectra
XRD spectraofoffilaments
filamentsshow
showonly
onlyamorphous
amorphousbands bandsand
andaaremarkable
remarkabledecrease
decreasein
in
the intensity of diffraction peaks relative to the raw materials (Figure 6A). However,
the intensity of diffraction peaks relative to the raw materials (Figure 6A). However, no no
major differences
major differencesareareshown
shownbetween
betweenthethe100PLA
100PLAfilament
filamentand
andthe
the95PLA/5CBSW
95PLA/5CBSW and and
90PLA/10CBSW filaments, indicating that the reticular parameters of the PLA
90PLA/10CBSW filaments, indicating that the reticular parameters of the PLA crystal struc-crystal
structure remained unchanged after coextrusion of the polymer with CBSW. Similar ob-
servations were also reported by Tran et al. 2017 for poly(ε-caprolactone) matrix biocom-
posites [17]. Therefore, to obtain information on the variation in the thermal properties of
composite filaments compared to pure materials, a DSC analysis was performed (Figure
6B). The DSC thermograms of the PLA-based biofilaments or PLA and CBSW-based fila-
Materials 2024, 17, 1260 8 of 14

Materials 2024, 14, x FOR PEER REVIEW 9 of 14

ture remained unchanged after coextrusion of the polymer with CBSW. Similar observations
were also reported by Tran et al. 2017 for poly(ε-caprolactone) matrix biocomposites [17].
Therefore, to obtain information on the variation in the thermal properties of composite
Leonard
filaments and Berrio,
compared on materials,
to pure the other hand,
a DSChighlighting
analysis wasthe same characteristic
performed (Figure 6B). in The
the
PLA-based filaments
DSC thermograms of and cocoa bean biofilaments
the PLA-based shells they have developed
or PLA and which filaments
and CBSW-based have not un- are
shown inany
dergone Figure 5B. The
chemical glass temperatures
treatment, (Tgexistence
attribute the ) of all materials
of two were
peaksmeasured using the
during melting to
inflection
the point:
different the Tg coincides
degradation with the
temperatures of point at whichand
hemicellulose the second derivative
cellulose present inis the
equal to
filler
zero. This
The Tlast ◦ C, a value similar to that reported
[18]. g measured for theseems
interpretation 100PLAto sample was 59.19 with
be in agreement the DSC curve of CBSW ob-
in the literature
tained in our study[1] and
andslightly
shown in lower
Figurethan
4B.that of the starting pellet.

Figure 6. (A) XRD diffractograms and (B) DSC curves of filaments.

Figure 6. (A) XRD diffractograms and (B) DSC curves of filaments.

3.3. Characterization
Composite filaments of 3D Samples
show a lower Tg than the PLA filament. This suggests that the
cocoaThree-dimensional
particles interactedspecimens
with the PLA foron a molecular
tensile testing scale.
were However,
producedthe by main differences
FFF printing in
due to this interaction
accordance process between
with ISO 527-2(2012) [26]. The theoverall
polymer chainsresults
average and theare filler
shownare found in the
in Figure 7.
crystallization
The results of the (T ) and melting
c pure PLA samples (T m ) temperatures. The crystallization temperature
are consistent with those reported in the literature T c in the
95PLA/5CBSW and 90PLA/10CBSW filaments compared to the 100PLA filament having a
[1].
Tc ofThe
124.39 ◦ C decreases to 110.92 ◦ C and 106.99 ◦ C, respectively. Furthermore, the melting
Young’s modulus (Et) increased in the CBSW-based samples. Indeed, an inevita-
process
ble seems to of
consequence bethe
particularly
addition influenced
of filler to theby the presence
polymer of the
matrix CBSW
is an filler,inwhich
increase leads
the viscos-
to the
ity development
of the polymer melt, of a double melt peak
which usually (Tm and
depends onTm1
the) in composite
volume fractionbiofilaments,
of filler and which
the
is absent in 100PLA (Figure 6B). Similar behaviour and the presence
size and shape of the particles (Figure 7A) [36]. Overall, the presence of filler appears toof the double melting
peak hindered
have were observed by the authors
the mobility in biocomposites
of the polymer chain of thebased
PLAon polylactic
matrix, acidincreasing
thereby and olive
wood waste, indicating a different behaviour during the phase transition
the stiffness of the 3D sample composite. Furthermore, this increase appears to be linear, between the
polymer and the organic filler [35].
as observed by the Et value increasing with filler wt.%. It has been reported in the scientific
Leonard
literature that and Berrio, on
the addition of the otheractually
the filler hand, highlighting
modifies thethe same characteristic
polymer phase and thein the
poly-
PLA-based filaments and cocoa bean shells they have developed
mer interacts with the filler surface to form an adsorbed polymer interphase [36]. The and which have not
undergone
thickness ofany
this chemical
interphase treatment,
(as well as attribute
the value theofexistence
the Young’sof two peaks depends
modulus) during melting
on the
to the different degradation temperatures of hemicellulose
bond between the polymer and the filler, which in turn depends on the surface and cellulose presentareain(i.e.,
the
filler [18]. This last interpretation seems to be in agreement with the
the shape and size of the filler particles). Based on these considerations, the different be-DSC curve of CBSW
obtained in our study and shown in Figure 4B.
haviours of the composites could probably be due to a stronger interaction between the
polymer and the filler
3.3. Characterization in Samples
of 3D the 90PLA/10CBSW_3D sample, caused by the larger specific
active surface area of the CBSW particles, as well as the higher volume fraction of the filler
Three-dimensional specimens for tensile testing were produced by FFF printing in
[36].
accordance with ISO 527-2(2012) [26]. The overall average results are shown in Figure 7.
The elongation at break εt (%) always decreases with the addition of filler to pure
The results of the pure PLA samples are consistent with those reported in the literature [1].
PLA (Figure 7B), in agreement with the literature [17,30], leading to an increase in the
fragility of the composites compared to the polymer. Similarly, the value of the maximum
strength σt (MPa) decreases in both the 95PLA/5CBSW_3D and 90PLA/10CBSW_3D sam-
ples (Figure 7C) with a non-linear trend. This is probably due to a different orientation of
the filler particles dispersed in the polymer matrix. Overall, the tensile test results show a
lower ductility and a change in the mechanical properties of CBSW based composites; the
non-uniform distribution of CBSW particles in the composite structure is the main cause.
Materials2024,
Materials 2024,17,
14,1260
x FOR PEER REVIEW 109 of
of 14
14

Figure
Figure 7. Mechanical properties
7. Mechanical propertiesfrom
fromtensile
tensiletests
testsofof3D3Dsamples:
samples: (A)
(A) Young’s
Young’s modulus
modulus Et (GPa),
Et (GPa), (B)
(B) elongation
elongation at break
at break εt (%),
εt (%), (C)(C) maximum
maximum strength
strength (MPa).
(MPa).

The
TheYoung’s modulus
DSC analysis (Et) increased
performed on theinFFF
the printed
CBSW-based samples.
3D samples Indeed,in
is shown anFigure
inevitable
8. A
consequence of the addition of filler to the polymer matrix is an increase
decrease in glass transition temperature (Tg) is observed for all 3D samples compared in the viscosity to
of the polymer melt, which usually depends on the volume fraction
the pure PLA 3D sample. The crystallization (Tc) and melting temperatures (Tm and Tm1) of filler and the size
and shape
of the of the particles
CBSW-based (Figure
samples 7A) [36].but
also decrease Overall,
remain thehigher
presence
thanofthose
fillermeasured
appears tofor have
the
hindered the mobility of the polymer chain of the PLA matrix, thereby increasing the
corresponding composite filaments, indicating a greater interaction between the polymer
stiffness of the 3D sample composite. Furthermore, this increase appears to be linear, as
chains and the filler and a higher degree of crystallinity after the printing process. This
observed by the Et value increasing with filler wt.%. It has been reported in the scientific
also explains the increase in Young’s modulus of the CBSW-based 3D samples described
literature that the addition of the filler actually modifies the polymer phase and the polymer
above. There is also always a double melting peak in 3D samples due to the presence of
interacts with the filler surface to form an adsorbed polymer interphase [36]. The thickness
the filler in the polymer matrix, i.e., different phases.
of this interphase (as well as the value of the Young’s modulus) depends on the bond
between the polymer and the filler, which in turn depends on the surface area (i.e., the
shape and size of the filler particles). Based on these considerations, the different behaviours
of the composites could probably be due to a stronger interaction between the polymer and
the filler in the 90PLA/10CBSW_3D sample, caused by the larger specific active surface
area of the CBSW particles, as well as the higher volume fraction of the filler [36].
The elongation at break εt (%) always decreases with the addition of filler to pure
PLA (Figure 7B), in agreement with the literature [17,30], leading to an increase in the
fragility of the composites compared to the polymer. Similarly, the value of the maximum
strength σt (MPa) decreases in both the 95PLA/5CBSW_3D and 90PLA/10CBSW_3D
samples (Figure 7C) with a non-linear trend. This is probably due to a different orientation
of the filler particles dispersed in the polymer matrix. Overall, the tensile test results show
a lower ductility and a change in the mechanical properties of CBSW based composites; the
non-uniform distribution of CBSW particles in the composite structure is the main cause.
The DSC analysis performed on the FFF printed 3D samples is shown in Figure 8. A
decrease in glass transition temperature (Tg ) is observed for all 3D samples compared to
the pure PLA 3D sample. The crystallization (Tc ) and melting temperatures (Tm and Tm1 )
of the CBSW-based samples also decrease but remain higher than those measured for the
corresponding composite filaments, indicating a greater interaction between the polymer
chains and the filler and a higher degree of crystallinity after the printing process. This also
explains the increase in Young’s modulus of the CBSW-based 3D samples described above.
There is also always a double melting peak in 3D samples due to the presence of the filler
in the polymer matrix, i.e., different phases.
FigureTo8.better
DSC curves of 3D samples.
understand the printability of the developed biofilaments, a microscopic
analysis was performed along the side surface of the 3D samples. The images obtained by
To better understand
light microscopy are shownthe printability
in Figure 9 andof the developed
overall show good biofilaments,
adhesion betweena microscopic
the 3D
analysis was performed along the side surface of the 3D
layers in both the 100PLA_3D sample (Figure 9A) and in the 95PLA/5CBSW_3D samples. The images obtained
sample by
light microscopy are shown in Figure 9 and overall show good
(Figure 9B), in contrast to the 90PLA/10CBSW_3D sample (Figure 9C). The addition ofadhesion between the 3D
layers in
CBSW both
filler to the
the 100PLA_3D
polymer matrix,sample (Figure
which 9A)the
causes and in the 95PLA/5CBSW_3D
formation of particle aggregates samplein
(Figure
the 9B), causes
filament, in contrast to theproblems
adhesion 90PLA/10CBSW_3D samplein(Figure
between the layers 9C). The addition as
the 90PLA/10CBSW_3D; of
CBSW filler to the polymer matrix, which causes the formation of particle
in the other 3D samples, the layers are perfectly aligned with each other and do not show aggregates in
the filament, causes adhesion problems between the layers in the 90PLA/10CBSW_3D; as
in the other 3D samples, the layers are perfectly aligned with each other and do not show
 the pure PLA 3D sample. The crystallization (Tc) and melting temperatures (Tm and Tm1)
of the CBSW-based samples also decrease but remain higher than those measured for the
corresponding composite filaments, indicating a greater interaction between the polymer
Materials 2024,
chains17, 1260
and the filler and a higher degree of crystallinity after the printing process. This 10 of 14

also explains the increase in Young’s modulus of the CBSW-based 3D samples described
above. There is also always a double melting peak in 3D samples due to the presence of
swelling, deformation, or detachment; however, the presence of some air voids is observed,
the filler in the polymer
and thismatrix,
porosityi.e., different
probably phases.
inhibits the mechanical performance of the composite material.

Figure 8. DSC curvesFigure

of 3D8. samples.
DSC curves of 3D samples.

3.4. From Agro-Industrial

To better understand the printability Wasteof
to New
the Objects
developed biofilaments, a microscopic
In this work, the waste
analysis was performed along the side surface of the materials, i.e.,
3D cocoa bean shell
samples. Thewaste
imagesCBSW, were supplied
obtained by
as a residue from the chocolate manufacturing process in the form of a coarse-grained,
light microscopy are shown in Figure 9 and overall show good adhesion between the 3D
non-homogeneous powder. These are residues from chocolate processing that the company
layers in both the must
100PLA_3D
necessarilysample
discard,(Figure 9A) andtime
with a significant in the
and95PLA/5CBSW_3D
economic effort. In thissample
section, the
(Figure 9B), in contrast
authorsto theto90PLA/10CBSW_3D
want sample
illustrate an example of one of the (Figure 9C). The
many sustainable additionthat
applications of can
CBSW filler to the polymer matrix, which causes the formation of particle aggregates in by
be imagined, i.e., reusing recycled materials to create a new object that can be redeployed
theadhesion
the filament, causes same company that produced
problems betweenthe the
waste. Basedinonthe
layers the90PLA/10CBSW_3D;
tested performance of theas devel-
oped cocoa and poly(lactic acid) biofilaments, the 90PLA/10CBSW filament was selected
in the other 3D samples, the layers are perfectly aligned with each other and do not show
for 3D printing the chocolate-shaped objects (prototypes) using Fused Filament Fabrication
3D printing technology (Figure 10). Specifically, the authors chose to produce 3D printed
objects in the shape of traditional chocolates or other shapes, so that they could be used by
the supplier company for display in the shop window or inside the shop as design and fur-
nishing objects, having greater durability and resistance to environmental conditions than
real chocolate. The final object after printing preserves the same environmental resistance
characteristics as the 3D bars tested in the previous paragraph. Most interestingly is that
already the 5 wt.% of cocoa powder (CSBW) product allows the organoleptic characteristics
of pure chocolate to be preserved in the 3D object, giving customers the feeling that it is a
real product exhibited in a store window.
 swelling, deformation, or detachment; however, the presence of some air voids is
Materials 2024, 17, 1260 served, and this porosity probably inhibits the mechanical performance of the
11 of 14 compo
material.

9.Magnified
Figure 9.
Figure Magnifiedimages (50 (50
images X) ofX)
the
of3D
thebars:
3D (A) printing
bars: surface of
(A) printing the 100PLA_3D
surface specimen; specim
of the 100PLA_3D
(B) printing surface of the 95PLA/5CBSW_3D specimen; (C) printing of surface
(B) printing surface of the 95PLA/5CBSW_3D specimen; (C) printing surface the of
90PLA/10CBSW_3D specimen.
90PLA/10CBSW_3D specimen.

3.4. From Agro-Industrial Waste to New Objects

In this work, the waste materials, i.e., cocoa bean shell waste CBSW, were supp
as a residue from the chocolate manufacturing process in the form of a coarse-grain
non-homogeneous powder. These are residues from chocolate processing that
 ronmental conditions than real chocolate. The final object after printing preserves the
same environmental resistance characteristics as the 3D bars tested in the previous para-
graph. Most interestingly is that already the 5 wt.% of cocoa powder (CSBW) product
allows the organoleptic characteristics of pure chocolate to be preserved in the 3D object,
Materials 2024, 17, 1260
giving customers the feeling that it is a real product exhibited in a store window. 12 of 14

Figure
Figure10.
10.Manufactured
Manufactured filament (A),(A),
filament CAD model
CAD created
model with with
created Rhinoceros version
Rhinoceros 7 software
version (Rob-
7 software
ert McNeel & Associates, Seattle, DC, USA) (B) and representative printed samples (C).
(Robert McNeel & Associates, Seattle, DC, USA) (B) and representative printed samples (C).

4.4.Conclusions
Conclusions
In
Inthis
thisstudy,
study, novel
novel green
green composite
compositefilaments
filamentsforforFFF
FFFwere
weredeveloped
developedand andcharac-
charac-
terized,
terized,utilizing
utilizingcocoa
cocoa bean
bean shell
shell waste
waste and
and polylactic
polylactic acid.
acid. Structural–morphological,
Structural–morphological,
thermal,
thermal, and
and mechanical characterization
characterization of ofboth
bothraw
rawmaterials
materialsand
andproducts
products (extruded
(extruded fil-
filaments
aments and and3D3Dprinted
printed specimens)
specimens) was
was comprehensively
comprehensively conducted.
conducted. Overall,
Overall, thethe find-
findings
ings revealed
revealed significant
significant fillerfiller aggregates
aggregates at 10at wt.%
10 wt.% CBSW
CBSW concentration
concentration in the
in the PLAPLA ma-
matrix.
trix. However,
However, at both
at both CBSW CBSW concentrations
concentrations (5 wt.% (5 and
wt.%10and 10 wt.%),
wt.%), no notable
no notable morpho-
morphological or
thermal
logical oralterations were observed,
thermal alterations and satisfactory
were observed, printability
and satisfactory was achieved.
printability Moreover,
was achieved.
tensile tests
Moreover, on thetests
tensile 3D printed
on the 3D objects demonstrated
printed enhanced rigidity
objects demonstrated enhanced in rigidity
these specimens
in these
and better load resistance at the highest CBSW concentrations. Finally,
specimens and better load resistance at the highest CBSW concentrations. Finally, the bio- the biofilament
exhibiting
filament superiorsuperior
exhibiting properties (containing
properties the 10 wt.%
(containing of CBSW)
the 10 wt.% ofwas utilized
CBSW) was to fabricate
utilized to
some simple
fabricate some3D printed
simple 3D chocolate models, models,
printed chocolate showcasing the efficacy
showcasing of the proposed
the efficacy of the pro-ap-
proachapproach
posed in successfully recycling agro-industrial
in successfully waste within
recycling agro-industrial the same
waste withinproduction
the same company,
produc-
leading
tion to economic
company, leadingand ecological
to economic benefits.
and ecological Future research
benefits. endeavors
Future aim to identify
research endeavors aim
biomarkers confirming the longevity of cocoa organoleptic properties
to identify biomarkers confirming the longevity of cocoa organoleptic properties post-post-printing process
and investigate
printing processthe anddurability
investigate of biocomposites
the durabilityunder controlled environmental
of biocomposites under controlledconditions.
envi-
ronmental conditions.
Author Contributions: Conceptualization, C.E.C.; software, V.D.C. and D.R.; validation, C.E.C. and
D.F.; formal
Author analysis, D.F.
Contributions: and D.R.; data C.E.C.;
Conceptualization, curation, C.E.C.,V.D.C.
software, D.F. and
andD.R.;
D.R.;writing—original
validation, C.E.C. draft
and
preparation, C.E.C., D.F. and D.R.; writing—review and editing, C.E.C., D.F. and D.R.; visualization,
D.F.; formal analysis, D.F. and D.R.; data curation, C.E.C., D.F. and D.R.; writing—original draft
C.E.C., D.F. C.E.C.,
preparation, and D.R.;
D.F.supervision, C.E.C., D.F. and
and D.R.; writing—review D.R.
and All authors
editing, C.E.C., have readD.R.;
D.F. and andvisualization,
agreed to the
published version of the manuscript.
C.E.C., D.F. and D.R.; supervision, C.E.C., D.F. and D.R. All authors have read and agreed to the
published
Funding: version of the manuscript.
This research was funded by Ministero dell’Istruzione dell’Università e della Ricerca
(project PON R&I 2014–2020, D.M. 1061 del 10/8/2021-37◦ ciclo-Azione IV.5, Dottorati su Tematiche
Green, 2021).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Acknowledgments: The authors thank the company “Maglio Arte Dolciaria S.R.L.” (Maglie, Lecce,
Italy) for providing the recycled raw material.
Conflicts of Interest: The authors declare no conflicts of interest.

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