materials

Article
Mechanical and Physicochemical Properties of 3D-Printed
Agave Fibers/Poly(lactic) Acid Biocomposites
Valeria Figueroa-Velarde, Tania Diaz-Vidal, Erick Omar Cisneros-López , Jorge Ramón Robledo-Ortiz ,
Edgar J. López-Naranjo, Pedro Ortega-Gudiño and Luis Carlos Rosales-Rivera *

University Center of Exact Sciences and Engineering (CUCEI), University of Guadalajara,

Guadalajara 44430, Mexico; [email protected] (V.F.-V.); [email protected] (T.D.-V.);
[email protected] (E.O.C.-L.); [email protected] (J.R.R.-O.);
[email protected] (E.J.L.-N.); [email protected] (P.O.-G.)
* Correspondence: [email protected]; Tel./Fax: +52-3313-7859-00 (ext. 27590)

Abstract: In order to provide a second economic life to agave fibers, an important waste material
from the production of tequila, filaments based on polylactic acid (PLA) were filled with agave
fibers (0, 3, 5, 10 wt%), and further utilized to produce biocomposites by fused deposition model-
ing (FDM)-based 3D printing at two raster angles (−45◦ /45◦ and 0◦ /90◦ ). Differential scanning
calorimetry, water uptake, density variation, morphology, and composting of the biocomposites
were studied. The mechanical properties of the biocomposites (tensile, flexural, and Charpy impact
properties) were determined following ASTM international norms. The addition of agave fibers to





 the filaments increased the crystallinity value from 23.7 to 44.1%. However, the fibers generated
porous structures with a higher content of open cells and lower apparent densities than neat PLA
Citation: Figueroa-Velarde, V.;
pieces. The printing angle had a low significant effect on flexural and tensile properties, but directly
Diaz-Vidal, T.; Cisneros-López, E.O.;
Robledo-Ortiz, J.R.; López-Naranjo,
affected the morphology of the printed biocomposites, positively influenced the impact strength,
E.J.; Ortega-Gudiño, P.; Rosales- and slightly improved the absorption values for biocomposites printed at −45◦ /45◦ . Overall, increas-
Rivera, L.C. Mechanical and ing the concentrations of agave fibers had a detrimental effect on the mechanical properties of the
Physicochemical Properties of biocomposites. The disintegration of the biocomposites under simulated composting conditions was
3D-Printed Agave Fibers/Poly(lactic) slowed 1.6-fold with the addition of agave fibers, compared to neat PLA.
Acid Biocomposites. Materials 2021,
14, 3111. https://doi.org/10.3390/ Keywords: agave fibers; 3D printing; fused deposition modeling; poly(lactic) acid; biocomposites
ma14113111

Academic Editor: Stephan Rudykh

1. Introduction
Received: 28 April 2021
Accepted: 1 June 2021
Among the available rapid prototyping or additive manufacturing technologies,
Published: 5 June 2021
printing based on fused deposition modeling (FDM) using thermoplastics is the best
for modeling possibilities, mainly due to its simplicity, versatility, low economic im-
Publisher’s Note: MDPI stays neutral
pact, and widespread applicability [1]. FDM, also known as 3D printing, allows three-
with regard to jurisdictional claims in
dimensional figures to be obtained at high speed and precision, based on the extrusion of
published maps and institutional affil- a polymer filament in a layer-by-layer arrangement (X and Y axes) on top of a movable
iations. plate (z axis), until a 3D structure is obtained [2]. These complex figures can be produced
in less time, as the prior formation of a mold is not required [3]. FDM applications have
seen a predominant growth in personal prototyping fabrication, mainly due to a sharp cost
reduction of FDM machines [4]. However, commercial FDM applications are still leading
Copyright: © 2021 by the authors.
the market, mainly for the formation of automotive parts and aerospace prototypes [5],
Licensee MDPI, Basel, Switzerland.
electronic devices, house construction, among others [6,7]. Promising results have also
This article is an open access article
been found in the field of medicine for the production of biomedical devices and materials,
distributed under the terms and such as bone replacement scaffolds [8–10].
conditions of the Creative Commons Common polymer matrices employed in FDM techniques include acrylonitrile bu-
Attribution (CC BY) license (https:// tadiene styrene (ABS), polycarbonates (PC), polyamides, polystyrene (PS), polymethyl
creativecommons.org/licenses/by/ methacrylate (PMMA), polyethylene (PE), and polylactic acid (PLA) [11]. Recently, ef-
4.0/). forts have been focused on the production and use of sustainable and renewable bio-

Materials 2021, 14, 3111. https://doi.org/10.3390/ma14113111 https://www.mdpi.com/journal/materials

Materials 2021, 14, 3111 2 of 16

plastics (such as PLA) for a wide variety of applications, from packaging to engineering,
and biomedical devices, replacing petroleum-based plastics [12–14]. PLA is a thermo-
plastic biopolymer belonging to the family of aliphatic polyesters. PLA is obtained by
fermentation of renewable resources such as corn or agricultural waste [15]. Unlike other
polymers, PLA is considered a sustainable material as it can be compostable, which can
be further utilized to promote a new cycle of agricultural products for future conversion
into PLA [16].
The innate versatility of rapid prototyping enables the fabrication of high-resolution
parts reinforced with diverse materials such as ceramics, metals, minerals, and natural
fibers [6,17]. Traditional reinforcing materials such as glass or carbon fibers allow the
fabrication of composites with superior mechanical properties; however, their inherent
inconvenience relies on the difficulty of recycling their components once the material is
no longer purposeful [6]. In this sense, the addition of natural fibers as reinforcers in
composite materials has gained great attention due to their “green” character, cheaper cost,
and high availability [6,18]. The production of biocomposites from renewable sources,
recycled fibers, industrial co-products, and forestry and agricultural residues is an environ-
mentally friendly approach for the production of materials with a lower carbon footprint,
reducing the ecological impact of waste materials [6]. Fabrication of 3D-printed PLA-
based biocomposites using natural fibers includes bamboo powder [19], wood flour [20],
wood [21], kraft lignin [22], and cork [23], among others [24].
In 2020, the Tequila Regulatory Council estimated the production of 523,600 tons of
bagasse from Agave tequilana Weber var. Azul. Thus, 1.4 kg of agave waste is created per liter
of produced tequila [25,26], posing an extreme environmental issue. Several researchers
have joined efforts to find low-cost, environmentally friendly alternative uses to agave
wastes. Agave residues can be treated to obtain fibers that are typically short and elliptically
shaped, 10–12 cm long, and with a diameter of 592.34 µm [27]. Agave fibers have been
previously used for the obtaining of biocomposites. Torres-Tello produced biocomposites
from agave fibers and polyhydroxybutyrate (PHB) with increased tensile and flexural
moduli [28]. Recently, PLA- and agave fiber-reinforced biocomposites were produced by
dry-blending and rotational molding, demonstrating the production of biodegradable,
low-cost biocomposites [29]. However, to date, there have been no published reports
concerning reinforcement with agave fibers to produce filaments for an FDM process for a
final application in 3D printing. As agave fibers are waste material, the addition of waste
fibers to matrices, which are usually expensive, can help to diminish the cost of the material.
This offers the opportunity to generate novel materials suitable for 3D printing with certain
advantages, such as lightness, sustainability, biodegradability, and low cost (compared to
neat polymeric materials).
The present work describes the development of a biodegradable filled material for
further use as filaments in a 3D printer. Agave fibers (mesh 100–140) were used as a
filler material in a PLA matrix. The modified variables were weight percentage (0, 3, 5,
and 10 wt%) and FDM deposition angle (−45◦ /45◦ and 0◦ /90◦ ). Differential scanning
calorimetry (DSC), water uptake, density variation, and biodegradability of the biocom-
posites were studied, whereas morphological characterization was performed via SEM.
The mechanical properties were studied following the ASTM international norms for ten-
sile, flexural, and Charpy impact. The effects of FDM process parameters on the tensile
properties of fabricated agave fiber/PLA biocomposites were also investigated.

2. Materials and Methods

2.1. Materials
Polylactic acid 3251D (PLA, density = 1.24 g cm−3 , melt flow index = 80 g/10 min−1 ,
(2.16 kg, 210 ◦ C), according to the provided technical data sheet), supplied in spherical pel-
lets, was obtained from Nature Works LLC (Minnetonka, MN, USA). Agave fibers (AF) from
A. tequilana Weber var. Azul were obtained from a local tequila company (Mundo Agave,
Tequila, Mexico).
Materials 2021, 14, 3111 3 of 16

2.2. Agave Fiber Cleaning and Sieving

AF were prepared as reported by Pérez-Fonseca et al. [30] with minor modifications.
Briefly, the pithy fibers were hydrated for 24 h, and next, the pith was separated from the
fiber with a two-disk (diameter, 30 cm) Sprout-Waldron D2A509NH refiner (Muncey, PA,
USA). The separated AF were then centrifuged for 20 min at 3750× g rpm to remove excess
water, and dried outdoors. Finally, the AF were ground with a ball mill and sieved using a
Ro-Tap RX-29 (Oelde, Germany) with a #100–140 sieve fraction.

2.3. AF/PLA Filament Preparation

Samples of AF with different weight percentages (0, 3, 5, 10 wt%) and PLA were
prepared using a total weight of 1000 g for each composition (Table S1, Supplementary
Materials). Next, the materials were dry-blended using a high shear mixer JR Torrey
LP-12 (Monterrey, Mexico) for 2 min and oven-dried at 60 ◦ C for 24 h. The filaments
were then produced by extrusion using a twin-screw extruder Leistritz Micro 27 GL/GG
32D (Nuremberg, Germany) with a screw rotational speed of 65 rpm. A forward ramp
temperature profile with nine zones was set to 160/160/165/165/170/170/175/175/175 ◦ C.
The final filament had a diameter of 1.7 mm ± 0.07.

2.4. Differential Scanning Calorimetry (DSC)

A differential scanning calorimeter (TA Instruments Q100 (New Castle, DE, USA))
was used to study the thermal properties of the agave-fibers/PLA filaments. The spec-
imens were cut to a homogenous weight of 3–5 mg and heated once from 25 ◦
◦ − 1

to 200 C
(10 C min ) under nitrogen atmosphere. Glass transition temperature Tg , cold crys-
tallization temperature (Tcc ), melting temperature (Tm ), enthalpy of cold crystallization
(∆Hcc ), and melting enthalpy (∆Hm ) were determined from the DSC curves with TRIOS
TA software (Version 4.4.0.41651) [31]. Values of Tm and ∆Hm were obtained from the peak
temperature and area of the melting endotherm, respectively.
The crystallinity level (Xc ) of the samples was evaluated from their corresponding
melting enthalpies using Equation (1) [32],

∆Hm − ∆Hcc 100

Xc (%) = × (1)
∆H◦ w

where ∆H◦ (PLA) is the melting enthalpy (93.7 J g−1 ) of 100% crystalline (perfect crystal)
PLA, and w is the weight fraction of PLA in the biocomposites.

2.5. Fused Deposition Modeling/3D Printing

Computer aided designs (CAD) were drawn and visualized in Google SketchUp
(Version 16.0.14004, Mountain View, CA, USA) [33] with dimensions following the ASTM
standards for each test/characterization. The designs were transferred to a printable format
using the Hot-World GmbH & Co. Repetier-Host software [34] (Version 1.6.2, Willich,
Germany) and printed with a Wanhao Duplicator 4 (Jinhua, China), which has a layer
resolution of 100 µm, according to the provided user manual specifications. The maximum
printing size was 25 × 25 × 3 mm3 (length, width, and height, respectively) with a layer
height of 0.3 mm. The minimum resolution of the design and dimensions of the final pieces
are depicted in Figure S1, Supplementary Materials. The AF/PLA filaments with different
agave fiber weight percentages (0, 3, 5, 10 wt%) were printed using a nozzle temperature of
190 ◦ C, a bed temperature of 70 ◦ C and filled using a crosshatch pattern. The infill was set to
100%, with a crosshatch angle of −45◦ /45◦ and 0◦ /90◦ . The printing speed was 50 mm s−1 .
Materials 2021, 14, 3111 4 of 16

2.6. Density and Porosity

Experimental density ρexp , (g cm−3 ) calculations were performed for AF/PLA printed
pieces of 2.5 × 2.5 × 0.3 cm3 . The theoretical density was obtained from Equation (2).

1
Pth = xPLA xAF (2)
ρPLA + ρAF

where ρth is the theoretical density in g cm−3 , xPLA , xAF are the weight fraction of PLA and
AF, respectively, and ρPLA , ρAF are the experimental densities of PLA and AF, respectively,
obtained via a 3P Instruments gas pycnometer Ultrapyc 1200e (Odelzhausen, Germany)
with nitrogen in the chamber cell.
The porosity was calculated comparing the experimental and theoretical density as
in [35], using Equation (3). All the experiments were performed using four samples for
each composition.
ρth − ρexp
Porosity (%) = (3)
ρth

2.7. Water Absorption

The water absorption of AF/PLA printed composites was measured following the ASTM
D570-03 standard at room temperature. Prior, AF/PLA printed pieces of 25 × 25 × 3 mm3
were dried in an oven at 60 ◦ C and then weighed. Then, the samples were submerged in
distilled water and removed after 2, 4, 6, and 24 h for 50 days, cleaned of excess water with
a soft cotton cloth, and weighed for weight increment monitoring. All the experiments
were performed using four samples for each composition.

2.8. Mechanical Properties

Tensile tests were carried out following the ASTM International D638-03 standard
using type IV specimens. The testing was performed with an INSTRON 3345 (Norwood,
MA, USA) with a 5 kN load cell at a crosshead speed of 5 mm/min, subjecting a total of
8 specimens to uniaxial tensile stress.
Flexural properties were obtained according to the ASTM International D790-03
standard. The three-point flexural testing was performed with the same machine used for
tensile tests at a crosshead rate of 2 mm/min using 8 specimens of 70 × 12.7 × 3 mm3 .
Impact strength tests were carried out in a Charpy impact tester (Tinius Olsen IT104
(Horsham, PA, USA)) using a pendulum of 242 g (1.22 J). Printed pieces were prepared
according to the ASTM International D6110-04 standard. A manual sample notcher (In-
stron CEAST 6897 (Norwood, MA, USA)) was used to prepare the samples at least 24 h
before testing. Each value represents the average of 8 notched samples. All samples
were tested at room temperature (~25 ◦ C). The load direction applied on the specimens
with respect to the printing angle for the different mechanical tests is shown in Figure S2,
Supplementary Materials.

2.9. Disintegration under Simulated Composting Conditions

Gravimetric weight loss of AF/PLA printed pieces was performed following the ISO
standard 20200:2004. Initially, 25 × 25 × 3 mm3 pieces were oven-dried at 60 ◦ C, until a
constant weight was achieved. Then, the dried pieces were deposited under simulated
composting conditions, with 50% organic matter, 58 ◦ C and >40% of humidity for 49 days.
Every 7 days, the composted specimens were withdrawn, cleaned, dried at 60 ◦ C and
weighed again to study the material weight lost. All experiments were performed by
triplicate using 8 specimens for each composition.

2.10. Morphological Characterization

Micrographs were obtained with a field emission scanning electron microscope (FE-
SEM) (Tescan MIRA3 LMU (Brno, Czech Republic)) using a laser beam of 10 kV accelerating
Materials 2021, 14, 3111 5 of 16

voltage. Prior, the samples were immersed in liquid nitrogen, fractured, and then coated
with a thin conductive layer of Au under vacuum using an SPI Module Sputter Coater
(West Chester, PA, USA) for 60 s.

2.11. Statistical Analysis

The mechanical test data were subjected to an analysis of variance (ANOVA) to
determine if the differences were statistically significant (p ≤ 0.05) between the evaluated
factors and their levels. For each test, 8 repetitions were performed (8 specimens were
fractured), and the two end values were discarded.
A multifactorial design with two factors—fiber content and printing angle—was
designed with four and two levels, respectively. To analyze the behavior of the effects of
fiber content, printed angle, and their interactions, the mean comparison was analyzed
through the LSD test. The analyses were performed using Statgraphics Centurion XV
(The Plains, VA, USA) Version 15.2.06 [36].

3. Results and Discussion

3.1. SEM Micrographs of Agave Fibers and AF/PLA Filaments
The surface morphology of AF is detailed in Figure 1. AF were used without any
chemical treatment; therefore, impurities and debris can be observed in Figure 1A. Be-
fore filament preparation, the diameter and length of the AF were measured from SEM
micrographs. Properties such as fiber length and fiber orientation can alter the final mechan-
ical properties of a given composite [29]. Damaged fibers by compression-molding show a
steady reduction in fiber length, thus compromising its filler ability [37]. The measured area
was converted to an equivalent diameter of a circle to obtain the fiber diameter. Clean AF
(400 fibers counted, Figure 1A) showed an equivalent diameter of 46.6 ± 20.9 µm and a
length of 246 ± 92 µm (aspect ratio, L/D, of 5.2). After the sieving process (Figure 1B),
AF had a diameter of 37.7 ± 16.6 µm and a length of 255 ± 108 µm (capillary L/D ratio of
6.7). Sieved AF showed a difference in L/D aspect ratio compared to clean AF due to a
decrease in their diameter. After the extrusion process, the AF/PLA filaments with 10 wt%
agave content were frozen with liquid nitrogen, and then, the filament diameter (100 fibers
counted) was measured directly from cryofracture SEM micrographs (Figure 2). The ob-
tained diameter was 36.6 ± 16 µm. However, the fiber length in the final printed piece
could not be measured. Nonetheless, damage to some extent in the length is expected [37].

3.2. Thermal Properties and Crystallinity of Agave Fibers/PLA Filaments

Values for glass transition (Tg ), crystallization (Tc ) and melting temperatures (Tm )
were obtained from the DSC curves for neat PLA and AF/PLA filaments (Table 1). While Tg
and Tc values diminished with the addition of AF, Tm values of filaments showed a minor
increase with respect to PLA. The 0–3 wt% and 5–10 wt% AF/PLA filaments showed a 5%
and 11% reduction in Tc values, respectively, in comparison to neat PLA. Tg values for neat
PLA and 0 wt% AF/PLA filaments were similar (58.9 ◦ C and 59.1 ◦ C, respectively), whereas
Tg values for 3–10 wt% AF/PLA filaments showed no significant differences (57.9 ◦ C,
57.7 ◦ C, and 57.2 ◦ C for 3 wt%, 5 wt%, and 10 wt% AF/PLA composites, respectively).
The DSC thermal transitions for neat PLA and all AF/PLA filaments are detailed in
Figure S3, Supplementary Materials. The crystallinity values of PLA and AF/PLA filaments
were obtained from ∆Hc and ∆Hf values. After the extrusion process, the crystallinity
value of 0 wt% AF/PLA filaments increased from 11.6% to 23.7% (Table 1), which can
be attributed to the cooling rate of the filaments after the extrusion stage [38]. The low
crystallinity value observed for neat PLA pieces is explained by PLA stoichiometry (L and
D isomers) and the slow crystallization rate of PLA [39]. High D content gives amorphous
extruded materials. In this work, the low crystallinity value of PLA 3251 is due to the
presence of 1.4% of the D-isomer.
The crystallinity values of AF/PLA filaments were similar for biocomposites of be-
tween 0–3 wt% and 5–10 wt% AF content. However, the values increased up to 50% and up
 graphs. Properties such as fiber length and fiber orientation can alter the final mechanical
properties of a given composite [29]. Damaged fibers by compression-molding show a
steady reduction in fiber length, thus compromising its filler ability [37]. The measured
area was converted to an equivalent diameter of a circle to obtain the fiber diameter. Clean
Materials 2021, 14, 3111 AF (400 fibers counted, Figure 1A) showed an equivalent diameter of 46.6 ± 20.9 μm6 of and
16
a length of 246 ± 92 μm (aspect ratio, L/D, of 5.2). After the sieving process (Figure 1B), AF
had a diameter of 37.7 ± 16.6 μm and a length of 255 ± 108 μm (capillary L/D ratio of 6.7).
Sieved AF showed a difference in L/D aspect ratio compared to clean AF due to a decrease
to
in 71%
theirfor 0–3 wt%After
diameter. and 5–10 wt% AF content,
the extrusion process,respectively,
the AF/PLAcompared
filamentsto neat10PLA.
with wt%This ef-
agave
fect can be attributed to the nucleation effect caused by the presence of AF
content were frozen with liquid nitrogen, and then, the filament diameter (100 fibers[40]. Similarly,
Teixeira
counted)etwasal. found that after
measured adding
directly from10cryofracture
wt% of thermoplastic bagasse to
SEM micrographs PLA biocompos-
(Figure 2). The ob-
ites, their crystallinity increased from 1.6 to 17.5%, due to the presence
tained diameter was 36.6 ± 16 μm. However, the fiber length in the final of cellulosic
printed fibers
piece
from
couldcassava bagasse [41].
not be measured. Nonetheless, damage to some extent in the length is expected [37].

Figure 1. SEM
Figure 1. SEM micrographs
micrographs ofof agave
agave fibers
fibers (AF)
(AF) used
used for
for biocomposite
biocomposite preparation (A) after
after sieving,
sieving, and (B) after
after high
high
shear mixing
shear mixing process
process (100
(100×
× magnification).
magnification).

Figure 2. SEM micrographs of agave fibers/PLA biocomposites with different agave fiber content (0, 3, 5 and 10 wt%) and
angle deposition (−45◦ /45◦ and 0◦ /90◦ ) (70× magnification).

3.3. FDM Deposition Angle and Agave Fiber Content

In FDM, variables such as printing speed, printing temperature, layer thickness,
and pattern, among others, directly influence the quality and mechanical properties of the
final fabricated pieces [2,42]. In the present work, AF/PLA biocomposites were printed
horizontally since higher mechanical properties have been reported for printed pieces in
this particular direction with the presence of a contour layer in all cases [2,43,44].
Figure 2 shows the SEM micrographs of the printed pieces at different printing angles
and AF content. In pieces printed at 0◦ /90◦ , the fracture has a characteristic transverse
Materials 2021, 14, 3111 7 of 16

shape, parallel to the printing threads. The layer thickness value obtained at 0◦ /90◦ was
close to the specified printing value (0.3 mm) and diminished to 0.26 mm when the AF
content increased to 10 wt%. The thickness at −45◦ /45◦ had an average of 0.27 mm
(Table S1, Supplementary Materials). However, the thicknesses of the AF/PLA biocom-
posites printed at −45◦ /45◦ were measured with a higher error due to the fusion of the
adjacent layers. In addition, a change in morphology was observed in specimens printed
using both configurations −45◦ /45◦ and 0◦ /90◦ , which is directly proportional to the
increase in fiber content.

Table 1. Thermal properties and crystallinity values of the filaments.

Agave Fiber Crystallinity

Filament Tg (◦ C) Tcc (◦ C) Tm (◦ C) ∆Hcc (J g−1 ) * ∆Hm (J g−1 ) *
Content (wt%) (%)
Neat PLA 58.9 95.9 168.0 33.7 44.5 11.6
0 59.1 91.2 168.9 25.8 48.0 23.7
Agave
3 57.9 91.8 169.3 25.3 46.1 22.9
fiber/PLA
5 57.7 85.2 168.0 12.6 49.7 41.7
filament
10 57.2 84.7 169.0 11.4 48.5 44.1
* The enthalpy values were normalized for the polymer content.

3.4. Density and Porosity of Agave-Fiber/PLA Printed Biocomposites

Printed biocomposites with 0 wt% AF/PLA showed 7% and 7.5% porosity attributed
to the interstices formed between the printing threads in the FDM process (Table 2). This is-
sue is intrinsically related to the FDM technique, and the presence of voids is expectedly
higher than the obtained with pieces fabricated with other processing methods, such as
injection molding [24]. In addition to the process parameters, variables such as material
composition, printing angle, and printing speed greatly influence the final porosity of the
biocomposites. For example, the porosity values of 3D-printed carbon fibers in ABS com-
posites were found to be highly dependent on the printing angle, and specimens printed
at 0◦ /90◦ showed much more porosity compared to specimens printed at −45◦ /45◦ [45].
In this work, the highest AF content tested for AF/PLA biocomposites printed at −45◦ /45◦
caused an increase in porosity by 2.8-fold (7.0% ± 1.9 to 20.1% ± 0.5 for biocomposites
with 0 wt% and 10 wt% AF, respectively) and 2.9-fold for biocomposites printed at 0◦ /90◦
(7.5% ± 0.8 to 21.9% ± 1.3 for biocomposites with 0 wt% and 10 wt% AF, respectively).
Thus, higher concentrations of AF strongly influenced the porosity of the final biocompos-
ites rather than the raster angle. The presence of natural fibers on polymeric composites is
known to induce the formation of porous structures due to the chemical incompatibility
between the used materials, also known as interfacial voids [29,46]. This is expected to
negatively affect the mechanical properties, as the filler capacity is reduced [47].

Table 2. Effect of agave fiber content on apparent density and porosity of the agave fibers/PLA printed pieces.

−45◦ /45◦ 0◦ /90◦

Agave Fiber Theoretical
Content (wt%) Density (g cm−3 ) Experimental Experimental
Porosity (%) Porosity (%)
Density (g cm−3 ) Density (g cm−3 )
0 1.247 1.159 ± 0.023 7.0 ± 1.9 1.153 ± 0.009 7.5 ± 0.8
3 1.248 1.104 ± 0.024 11.5 ± 1.9 1.135 ± 0.015 9.0 ± 1.2
5 1.249 0.989 ± 0.016 20.8 ± 1.3 1.042 ± 0.007 16.6 ± 0.6
10 1.250 0.999 ± 0.006 20.1 ± 0.5 0.976 ± 0.017 21.9 ± 1.3

Similarly, apparent experimental densities of biocomposites decreased with increased

AF percentages for biocomposites printed at −45◦ /45◦ (1.159 g cm−3 ± 0.023 to 0.999 g cm−3
± 0.006 for specimens with 0 wt% and 10 wt% AF, respectively) and 0◦ /90◦ (1.153 g cm−3
± 0.009 to 0.976 g cm−3 ± 0.017 for specimens with 0 wt% and 10 wt% AF, respectively)
(Table 2). The presence of voids and fibers can be observed in Figures S4 and S5, Sup-
Materials 2021, 14, 3111 8 of 16

plementary Materials. As the mass fraction of the AF is lower compared to the mass
fraction of PLA, the global contribution of fibers in the density of the biocomposites is not
significant; therefore, the density of the composite is expected to be similar to that of PLA
(1.246 and 1.278 g cm−3 , respectively). However, the density value of AF is still signifi-
cantly lower than that of conventional reinforcements, such as fiberglass (density value
of 2.55 g cm−3 ) [48]. Pérez-Fonseca et al. produced biocomposites with AF and pine fiber
with polypropylene as the matrix, reporting that as the natural fiber content increased,
the density of the fabricated composite also decreased [49].

3.5. Water Absorption

Water absorption is a process where multiple factors intervene, such as the homogene-
ity of the sample, the presence of fibers, and the presence of voids within the pieces [50].
Specimens fabricated from PLA can be susceptible to increased water absorption, as the
polar bonds of PLA may decompose in the presence of water, thus changing the mechanical
properties of the final piece [51]. Figure 3 shows the gained weight versus t1/2 curves of
FDM printed AF/PLA biocomposites at different percentages and two printing angles.
A rapid increase in water absorption is observed until 150 h, followed by a saturation
after 1225 h, except for 5 and 10 wt% AF/PLA biocomposites. A similar behavior is also
observed for biocomposites of kenaf bast fiber and PLA [52]. A strong correlation of the
printing angle with water absorption is observed for biocomposites with 3% and 5% AF.
In these cases, the water absorption was superior for pieces printed at −45◦ /45◦ . In con-
trast, for 10 wt% AF/PLA biocomposites printed at 0◦ /90◦ , the water uptake was higher
than that for biocomposites printed at −45◦ /45◦ . Natural fibers can form gaps, voids,
and cracks because of fiber swelling. Thus, water is expected to flow through the gaps via
capillary action [52]. This could explain the increased values of water uptake showed for
specimens with 10 wt% AF.
The -OH groups of AF should increase the hydrophilicity of the final material, as these
groups attract water molecules via hydrogen and van der Waals bonds [53]. This effect
was observed with sisal fiber/PLA biocomposites, which showed a 3.7-fold increase in
water absorption compared to neat PLA, due to the presence of the highly hydrophilic
sisal fibers [54]. Similarly, Le Duigou et al. demonstrated that increasing porous structures
and voids have a more pronounced effect on water absorption than the sole presence of
natural fibers [55]. However, we observed that water uptake values did not correlate with
increasing AF content. Instead, the tendency matched the amount of porosity present in
the material, which in turn correlated with the printing angle.

3.6. Tensile Properties

Increasing fiber content caused a decrease in the tensile properties of 3D-printed
AF/PLA biocomposites, as shown in Figure 4. FDM printed biocomposites with 0 wt% AF
had similar tensile strength and modulus values for both printed angles (~51 MPa). The low-
est tensile strength value was recorded for biocomposites with 5 wt% AF at −45◦ /45◦
(31 MPa), and biocomposites with 10 wt% AF/PLA at 0◦ /90◦ (28 MPa), which represents a
1.8-fold decrease in the tensile strength compared to neat PLA pieces.
It should be noted that the tensile strength values obtained for 10 wt% AF/PLA printed
biocomposites (28 MPa) are higher compared to the values of biocomposites processed
with different techniques, i.e., compression molding of AF/PHB (14 MPa) and AF/LMDPE
biocomposites (13 MPa) [28,56]. In contrast, compared to other natural fiber fillers for FDM
processes, AF are better filler options than wood flour/PLA composites [20], wood/PLA
composites [21], and cork/PLA composites [23]. Nevertheless, the mechanical behavior
of AF/PLA is lower compared to reinforced sugarcane bagasse fiber/PLA biocomposites
(tensile strength of 55 MPa with 6 wt% fiber content) [57].
Similarly, the tensile modulus decreased with the increasing AF content of printed
specimens at 0◦ /90◦ . At 10 wt% AF, the tensile value was 1.25-fold lower (880 MPa)
compared to that of 0 wt% AF. For specimens printed at −45◦ /45◦ , the tensile modulus
Materials 2021, 14, 3111 9 of 16

values decreased from 0 to 5 wt%, reaching a minimum at 5 wt% AF (825 MPa). Finally,
at 10 wt% AF content, the tensile modulus value increased by 1.1-fold (900 MPa) in
comparison to specimens with 5 wt% AF.
The addition of natural fibers is expected to increase the stiffness (tensile modulus)
of a given composite as observed by compression and injection techniques [40,56]. Ten-
sile modulus values for PLA are around 1700 MPa processed by rotational molding [29,38],
and 2300 MPa for injection [40,58]. By FDM, a lower tensile modulus value was obtained
Materials 2021, 14, x FOR PEER REVIEW 9 of 17
for neat PLA (1100 mPa), probably due to a higher porosity and a different crystallinity
value of the final material caused by the FDM process [59].

Waterabsorption
Figure 3. Water absorptionofofagave
agave fibers/PLA
fibers/PLA printed
printed biocomposites
biocomposites at different
at different agave
agave fiber fiber
per-
centages (0, (0,
percentages 3, 5,
3, and 1010
5, and wt%) and
wt%) and(A)
(A)printing
printingangle −45◦ /45and
angleofof−45°/45°, ◦ , and
(B)(B)
printing angle
printing 0◦ /90◦ .
angleofof0°/90°.

3.7. FlexuralProperties
3.6. Tensile Properties
Figure 5
Increasingshows
fiberthe obtained
content flexural
caused propertiesinfor
a decrease AF/PLA
the tensile biocomposites at different
properties of 3D-printed
raster
AF/PLA angles. In general,
biocomposites, asthe addition
shown of fibers
in Figure hadprinted
4. FDM a detrimental effect on
biocomposites the0 flexural
with wt% AF
strength values,
had similar regardless
tensile strengthofand
the printing
modulusangle.
valuesThe
formaximum flexural
both printed strength
angles value was
(~51 MPa). The
observed whenstrength
no AF were −45 ◦ /45◦
lowest tensile valueused
was(0recorded
wt% AFfor biocomposites,
biocomposites 87with
and 82 MPaAF
5 wt% forat −45°/45°
and 0◦ /90and
(31 MPa),
◦ , respectively), followed by biocomposites with 3 wt% AF for both printing
biocomposites with 10 wt% AF/PLA at 0°/90° (28 MPa), which represents a
angles for −45 ◦ /45◦ and 0◦ /90◦ , respectively). The flexural strength
1.8-fold(79 and 77inMPa
decrease the tensile strength compared to neat PLA pieces.
values of biocomposites printed at −45◦ /45◦ with 5 wt% and 10 wt% AF/PLA decreased
by 28 MPa compared to biocomposites with 0 wt% AF (87 MPa compared to 59 MPa).
Biocomposites printed at 0◦ /90◦ with 10 wt% AF showed the lowest flexural strength
value recorded (51 MPa), which represents a 1.7-fold decrease compared to biocomposites
Materials 2021, 14, 3111 10 of 16

printed
Materials 2021, 14, x FOR PEER REVIEW at the same angle and no fibers present. Similar results have been observed10for
of 3D-
17
printed sugarcane bagasse fiber/PLA composites [57] and rice straw/ABS composites [42],
where flexural properties decrease as fiber concentration increases.

Materials 2021, 14, x FOR PEER REVIEW 11 of 17

printed at the same angle and no fibers present. Similar results have been observed for
3D-printed sugarcane bagasse fiber/PLA composites [57] and rice straw/ABS composites
[42], where flexural properties decrease as fiber concentration increases.
Similarly, the flexural modulus diminished with the addition of fibers, and the rec-
orded values were similar for both raster angles. At −45°/45°, 0 wt%, and 3 wt% AF/PLA
biocomposites showed flexural modulus values around 3100 MPa, while the minimum
flexural modulus value of 2500 MPa was obtained with 5% AF pieces. However, 3 wt%
AF/PLA biocomposites printed at 0°/90° showed an increase by 94 MPa in the flexural
modulus compared with biocomposites with 0 wt% AF/PLA (3374 compared to 3280
(A)Tensile
Figure4.4.(A)
Figure strengthMPa).
Tensile strength The
and (B) lowest
tensile flexural
modulus
modulus of modulus
ofprinted
printed value
agave
agave (2350 MPa)
fibers/PLA
fibers/PLA was observed
biocomposites.
biocomposites.The for specimens
Theletters
lettersa–e
a–eonontop printed
of
top
ofthe
thebars
barsindicates
indicatessignificantwith
significant 5 wt%(pAF
differences
differences (p and
< <0.05). 0°/90°.
0.05).

It should be noted that the tensile strength values obtained for 10 wt% AF/PLA
printed biocomposites (28 MPa) are higher compared to the values of biocomposites pro-
cessed with different techniques, i.e., compression molding of AF/PHB (14 MPa) and
AF/LMDPE biocomposites (13 MPa) [28,56]. In contrast, compared to other natural fiber
fillers for FDM processes, AF are better filler options than wood flour/PLA composites
[20], wood/PLA composites [21], and cork/PLA composites [23]. Nevertheless, the me-
chanical behavior of AF/PLA is lower compared to reinforced sugarcane bagasse fi-
ber/PLA biocomposites (tensile strength of 55 MPa with 6 wt% fiber content) [57].
Similarly, the tensile modulus decreased with the increasing AF content of printed
specimens at 0°/90°. At 10 wt% AF, the tensile value was 1.25-fold lower (880 MPa) com-
pared to that of 0 wt% AF. For specimens printed at −45°/45°, the tensile modulus values
decreased from 0 to 5 wt%, reaching a minimum at 5 wt% AF (825 MPa). Finally, at 10
wt% AF content, the tensile modulus value increased by 1.1-fold (900 MPa) in comparison
to specimens with 5 wt% AF.
The addition of natural fibers is expected to increase the stiffness (tensile modulus)
of a given composite as observed by compression and injection techniques [40,56]. Tensile
modulus values for PLA are around 1700 MPa processed by rotational molding [29,38],
and 2300 MPa for injection [40,58]. By FDM, a lower tensile modulus value was obtained
for neat PLA (1100 mPa), probably due to a higher porosity and a different crystallinity
Figure5.5. (A)
Figure (A) Flexural
Flexuralstrength
strength
value and
and (B)
of(B) flexural
theflexural moduluscaused
modulus
final material ofofprinted
printed agave
byagave
the fibers/PLA
fibers/PLA
FDM biocomposites.
biocomposites.
process [59]. Theletters
The lettersa–f
a–fon
ontop
top of
thethe
of bars indicates
bars significant
indicates differences
significant (p(p
differences < 0.05).
< 0.05).
3.7. Flexural Properties
Similarly,
Although the 0 wt%flexural
AF/PLAmodulus diminished
biocomposites with flexural
showed the addition
strengthof fibers,
valuesand the
slightly
Figure
recorded 5 shows
values the
were obtained
similar flexural
for both properties
raster angles.for AF/PLA
At − 45 biocomposites
◦ /45 ◦ , 0 wt%, and
lower than those reported in the literature for different processing techniques, the ob- at differ-
3 wt%
ent raster
AF/PLA
tained angles.
flexural In general,
biocomposites
modulus the addition
showed
values flexural
were ofmodulus
higher fibers
thanhad
the atendency
detrimental
values around effect
3100 MPa,
observed on
forthe flexural
while
PLA the
pieces
strength
minimum values,
produced flexural regardless
via othermodulus of the printing
valuesuch
techniques, of 2500
as MPa angle. The maximum
was obtained
injection, rotationalwith flexural
5% AF and
molding, strength
pieces. value
However,
compression
was observed
3(2300,
wt% AF/PLA
3700 when
and no AFrespectively)
biocomposites
3100 MPa, wereprinted
used (0 at wt%
0◦ /90AF
[29,38,40]. biocomposites,
◦ showed an increase 87 byand9482MPaMPa in for
the
−45°/45°
flexural and
Themodulus0°/90°, respectively),
compared with
flexural properties observed followed
biocomposites by biocomposites
with 0 wt% printed
for the biocomposites with 3
AF/PLAin(3374 wt% AF for
compared
this work both
showedto
printing angles (79 and 77 MPa for −45°/45° and 0°/90°, respectively).
no dependence with the printing angle. However, other authors have observed a correla- The flexural strength
values of biocomposites
tion between printed
printing angle and at tensile
−45°/45° andwith 5 wt%strength,
flexural and 10 wt%with AF/PLA
a general decreased
decrease byin
28the
MPa compared to biocomposites with 0 wt% AF (87 MPa compared
values from −45°/45° to 0°/90°. For pieces printed at 0°/90°, only the layers printed at to 59 MPa). Bio-
composites printed
0° with respect at 0°/90°
to the axis arewith
those10 that
wt%support
AF showed the lowest
the tensile flexural
test, while thestrength value
ones at 90° had
recorded (51 MPa), which represents a 1.7-fold decrease compared
a minor effect opposing the pulling forces [59]. This behavior could be because for both to biocomposites
Materials 2021, 14, 3111 11 of 16

3280 MPa). The lowest flexural modulus value (2350 MPa) was observed for specimens
printed with 5 wt% AF and 0◦ /90◦ .
Although 0 wt% AF/PLA biocomposites showed flexural strength values slightly
lower than those reported in the literature for different processing techniques, the obtained
flexural modulus values were higher than the tendency observed for PLA pieces produced
via other techniques, such as injection, rotational molding, and compression (2300, 3700 and
3100 MPa, respectively) [29,38,40].
The flexural properties observed for the biocomposites printed in this work showed no
dependence with the printing angle. However, other authors have observed a correlation
between printing angle and tensile and flexural strength, with a general decrease in the
values from −45◦ /45◦ to 0◦ /90◦ . For pieces printed at 0◦ /90◦ , only the layers printed at 0◦
with respect to the axis are those that support the tensile test, while the ones at 90◦ had
a minor effect opposing the pulling forces [59]. This behavior could be because for both
printing angles (−45◦ /45◦ and 0◦ /90◦ ), a network of wires is formed perpendicularly to
each angle, which achieves a similar load distribution [60]. When pieces were built at a
single angle through all the layers, the load was distributed differently. Cole et al. (2016b)
produced pieces by varying the printing angle and found that pieces printed at 0◦ showed
greater tensile strength after those manufactured at 45◦ and 0◦ /90◦ , which may be because,
at 0◦ , the printing threads are oriented parallel to the applied load [44].

3.8. Impact Properties

In Figure 6, the impact strength for AF/PLA biocomposites as a function of AF content
and raster angle is depicted, where a positive correlation is observed for a raster angle of
−45◦ /45◦ . For biocomposites printed at −45◦ /45◦ , the impact strength value increased
by 3% for 3 wt% AF/PLA compared to neat PLA. Increasing the AF content to 10 wt%
decreased the impact strength by 1.1-fold with 27 J m−1 . In contrast, the impact resistance
values for specimens printed at 0◦ /90◦ decreased steadily with increased AF content,
reaching a minimum value of 26 J m−1 , with no significant difference compared to the
10 wt% AF/PLA printed at −45◦ /45◦ .
The properties of a biocomposite rely on the chemical and physical nature of matrix
and fibers. Increasing the fiber content in the AF/PLA biocomposites obtained in this work
decreased the impact resistance of the material. This is explained by a low fiber–matrix
compatibility causing defects and stress regions, which can be enhanced by the use of short
fibers [24,29].
In our case, this phenomenon was more pronounced with pieces printed at 0◦ /90◦ ,
with half of the printing threads in a parallel position to the crack propagation, which ab-
sorbs less energy [61].

3.9. Disintegration under Simulated Composting Conditions

The simulated composted conditions for specimens printed at −45◦ /45◦ showed no
changes in weight during the initial 15 days of the experiment (Figure 7), which could be
attributed to microbial lag and the adaptation to the hydrolysis of PLA chains, while the
small changes observed are attributed to weighting errors. After 21 days of composting,
losses of 5% in weight for 0, 3, and 5 wt% AF/PLA were observed, while 10 wt% AF/PLA
pieces showed a lag phase. These changes can be explained by the generation of small
oligomers and PLA monomers, which can be metabolized by microorganisms present in
the compost material. After 35 days, the weight loss was around 15% for all the printed
biocomposites, with no statistical differences. After 49 days of composting, 0 wt% AF/PLA
biocomposites showed the maximum weight loss (~27% weight loss), followed by biocom-
posites with 5 wt% and 10 wt% AF (~17% weight loss). In contrast, printed biocomposites
with 3 wt% AF had an average of 22% weight loss; however, the standard deviation ob-
served was 6%. The total weight loss after 50 days of 10 wt% AF/PLA specimens was
1.6-fold less than the weight loss observed for neat PLA specimens. These results can be
attributed to an increased crystallinity observed with increased AF contents, as crystalline
Materials 2021, 14, x FOR PEER REVIEW 12 of 17
Materials 2021, 14, 3111 12 of 16

3.8. Impact Properties

regionsIn Figure
are less6, susceptible
the impact strength for AF/PLA
to degradation than biocomposites
amorphous regions as a function
[62,63]. ofSimilarly,
AF con-
tent and raster angle is depicted, where a positive correlation is observed
Dong et al. obtained zero net weight losses with coir fiber/PLA from 6 to 12 days, with for a raster angle
an
of −45°/45°.
18.1% For biocomposites
reduction in weight lossprinted
after 18atdays
−45°/45°,
[64]. Inthethis
impact
case,strength value of
the presence increased by
coir fibers
3% for 3 wt%
increased AF/PLA
the weight compared
loss to neat
up to 34.9%, duePLA.
to theIncreasing the AF content
high hydrophilicity of theto 10 wt%
final compos-de-
creased
ites. Undertheenvironmental
impact strength by 1.1-fold
conditions, thewith 27 J m−1. Inofcontrast,
decomposition the impact
PLA to carbon resistance
dioxide, water,
values for specimens printed at 0°/90° decreased steadily with increased
and methane can take from several months up to 2 years [50]. On the other hand, the fact AF content,
reaching
that a minimum
the composites value
based onofAF26presented
J m−1, with no significant
a preserved difference
structure compared
after the to thetest
composting 10
wt% AF/PLA
could printed
be associated withat −45°/45°.
an increased PLA crystallinity and stiffness by thermal annealing
at theThe
testproperties
conditionsof(58 ◦ C) [40]. A brittle
a biocomposite rely on
PLA thecould
chemical andthe
explain physical nature of matrix
high fragmentation of
and fibers.
samples; inIncreasing theAF
this case, the fiber content
helped in the
to keep theAF/PLA
physicalbiocomposites
structure of theobtained
compositein this work
samples,
decreased
without the impact resistance
compromising of the material. This is explained by a low fiber–matrix
their biodegradability.
compatibility
Additionalcausing defects and of
optical micrographs stress regions, which
the disintegration canpieces
of the be enhanced
are shownbyinthe useS6,
Figure of
Supplementary
short fibers [24,29].Materials.

Figure 6. Charpy impact strength

strength of
of printed
printed agave
agave fibers/PLA biocomposites. The letters a–b on
fibers/PLA biocomposites. on top
top
significant differences
of the bars indicates significant differences (p
(p << 0.05).

In our case, this phenomenon was more pronounced with pieces printed at 0°/90°,
with half of the printing threads in a parallel position to the crack propagation, which
absorbs less energy [61].

3.9. Disintegration under Simulated Composting Conditions

The simulated composted conditions for specimens printed at −45°45° showed no
changes in weight during the initial 15 days of the experiment (Figure 7), which could be
attributed to microbial lag and the adaptation to the hydrolysis of PLA chains, while the
small changes observed are attributed to weighting errors. After 21 days of composting,
losses of 5% in weight for 0, 3, and 5 wt% AF/PLA were observed, while 10 wt% AF/PLA
pieces showed a lag phase. These changes can be explained by the generation of small
oligomers and PLA monomers, which can be metabolized by microorganisms present in
the compost material. After 35 days, the weight loss was around 15% for all the printed
biocomposites, with no statistical differences. After 49 days of composting, 0 wt% AF/PLA
 sites. Under environmental conditions, the decomposition of PLA to carbon dioxide, wa-
ter, and methane can take from several months up to 2 years [50]. On the other hand, the
fact that the composites based on AF presented a preserved structure after the composting
test could be associated with an increased PLA crystallinity and stiffness by thermal an-
Materials 2021, 14, 3111 13 of 16
nealing at the test conditions (58 °C) [40]. A brittle PLA could explain the high fragmen-
tation of samples; in this case, the AF helped to keep the physical structure of the compo-
site samples, without compromising their biodegradability.

Figure7.7.(A)
Figure (A)Percentage
Percentageweight
weightlosses
losses
ofof agave
agave fiber/PLAprinted
fiber/PLA printedbiocomposites
biocompositesunder
undersimulated
simulated
composting conditions and (B) photographs of agave fiber/PLA pieces after being composted.
composting conditions and (B) photographs of agave fiber/PLA pieces after being composted.

4. Conclusions
In this work, AF were extruded with PLA and the filaments were employed to prepare
AF/PLA biocomposites by FDM. After the extrusion process, the AF suffered mechanical
damage as the fiber diameter was reduced. The results herein indicated that the fiber con-
tent, rather than the raster angle, strongly influenced the crystallinity, porosity, flexural and
strength properties of the final biocomposites. In contrast, the raster angle influenced the
morphology and impact resistance of the printed biocomposites. This is highly significant
for future fabrications with FDM, as the choice of the natural fiber, with inherent features,
as well as the thermoplastic polymer, ultimately affects the characteristics and applicability
of the final piece. The fabricated AF/PLA printed biocomposites in this study have proven
to be a low-cost and compostable biocomposite, with lower disintegration rate and density
(lightweight). This feature can be useful for the fabrication of molds and 3D printing sup-
port materials based on AF, such as toys, which could be easily discarded and composted
after use.
Although further research is needed, AF can be employed as a component for 3D
printing, and the filling of PLA composites with natural fibers is an attractive, compostable,
and environmentally friendly alternative over traditional filler materials.
Materials 2021, 14, 3111 14 of 16

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/ma14113111/s1, Figure S1: Computer-aided designs (CAD) and their dimensions following
the ASTM standards for A) water absorption and biodegradation tests, (B) tensile tests, (C) flexural
tests, and D) impact tests; Figure S2: Load direction applied on the specimens with respect to the
printing angle for the different mechanical tests. (A) tensile, (B) flexural, and (C) impact; Figure S3:
Differential scanning calorimetry (DSC) thermograms of first heating for raw PLA and agave fiber
filaments; Figure S4: Scanning electron microscope (SEM) micrographs of the printed pieces showing
the presence of voids and fibers; Figure S5: Scanning electron microscope (SEM) micrographs of
agave fiber/PLA biocomposites printed at −45◦ /45◦ showing agave fiber details. (A) 0 wt% agave
fiber/PLA biocomposites, (B) 3 wt% agave fiber/PLA biocomposites, (C) 5 wt% agave fiber/PLA
biocomposites, and (D) 10 wt% agave fiber/PLA biocomposites; Figure S6: Optical micrographs of
agave fiber/PLA biocomposite pieces under simulated composting conditions obtained after being
weighed. Table S1: Formulation of biocomposites; Table S2: Layer thickness in cm for 3D-printed
agave fiber/PLA biocomposites at −45◦ /45◦ and 0◦ /90◦ measured from SEM micrographs.
Author Contributions: Conceptualization, V.F.-V. and L.C.R.-R.; methodology, V.F.-V., J.R.R.-O. and
L.C.R.-R.; software, V.F.-V., J.R.R.-O. and L.C.R.-R.; validation, E.O.C.-L., P.O.-G., J.R.R.-O. and
L.C.R.-R.; formal analysis, V.F.-V., J.R.R.-O., E.O.C.-L., T.D.-V. and L.C.R.-R.; investigation, V.F.-V.,
E.O.C.-L., and L.C.R.-R.; resources, E.O.C.-L., E.J.L.-N., P.O.-G., J.R.R.-O. and L.C.R.-R.; data curation,
V.F.-V. and L.C.R.-R.; writing—original draft preparation, T.D.-V. and L.C.R.-R.; writing—review
and editing, T.D.-V. and L.C.R.-R.; visualization, V.F.-V., T.D.-V. and L.C.R.-R.; supervision, J.R.R.-O.
and L.C.R.-R.; project administration, L.C.R.-R.; funding acquisition, E.J.L.-N., P.O.-G., J.R.R.-O. and
L.C.R.-R. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding. The authors are grateful to CONACYT
and Universidad de Guadalajara for the economic support. V.F.-V. would like to thank Consejo
Nacional de Ciencia y Tecnología (CONACYT) for her Ph.D. scholarship. We gratefully recognize a
postdoctoral fellowship for T.D.-V. from postdoctoral grants SEP-SES (23-007-C).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Matsuzaki, R.; Ueda, M.; Namiki, M.; Jeong, T.K.; Asahara, H.; Horiguchi, K.; Nakamura, T.; Todoroki, A.; Hirano, Y. Three-
dimensional printing of continuous-fiber composites by in-nozzle impregnation. Sci. Rep. 2016, 6, 23058. [CrossRef] [PubMed]
2. Chacón, J.M.; Caminero, M.A.; García-Plaza, E.; Núñez, P.J. Additive manufacturing of PLA structures using fused deposition modelling:
Effect of process parameters on mechanical properties and their optimal selection. Mater. Des. 2017, 124, 143–157. [CrossRef]
3. Ziemian, C.W.; Sharma, M.M.; Ziemian, S.N. Anisotropic Mechanical Properties of ABS Parts Fabricated by Fused Deposition
Modelling. Mech. Eng. 2012, 23, 2397.
4. Turner, B.N.; Strong, R.; Gold, S.A. A review of melt extrusion additive manufacturing processes: I. Process design and modeling.
Rapid Prototyp. J. 2014, 20, 192–204. [CrossRef]
5. Mohamed, O.A.; Masood, S.H.; Bhowmik, J.L. Experimental Investigations of Process Parameters Influence on Rheological
Behavior and Dynamic Mechanical Properties of FDM Manufactured Parts. Mater. Manuf. Process. 2016, 31, 1983–1994. [CrossRef]
6. Mohanty, A.K.; Vivekanandhan, S.; Pin, J.M.; Misra, M. Composites from renewable and sustainable resources: Challenges and
innovations. Science 2018, 362, 536–542. [CrossRef]
7. Bourmaud, A.; Beaugrand, J.; Shah, D.U.; Placet, V.; Baley, C. Towards the design of high-performance plant fibre composites.
Prog. Mater. Sci. 2018, 97, 347–408. [CrossRef]
8. Chia, H.N.; Wu, B.M. Recent advances in 3D printing of biomaterials. J. Biol. Eng. 2015, 9, 4. [CrossRef]
9. Lee Ventola, C. Medical applications for 3D printing: Current and projected uses. Pharm. Ther. 2014, 39, 704–711.
10. Gregor, A.; Filová, E.; Novák, M.; Kronek, J.; Chlup, H.; Buzgo, M.; Blahnová, V.; Lukášová, V.; Bartoš, M.; Nečas, A.; et al. Designing of
PLA scaffolds for bone tissue replacement fabricated by ordinary commercial 3D printer. J. Biol. Eng. 2017, 11, 31. [CrossRef]
11. Boparai, K.S.; Singh, R.; Singh, H. Development of rapid tooling using fused deposition modeling: A review. Rapid Prototyp. J.
2016, 22, 281–299. [CrossRef]
12. Mellinas, C.; Ramos, M.; Jiménez, A.; Garrigós, M.C. Recent trends in the use of pectin from agro-waste residues as a natural-based
biopolymer for food packaging applications. Materials 2020, 13, 673. [CrossRef]
Materials 2021, 14, 3111 15 of 16

13. Cataldo, V.A.; Cavallaro, G.; Lazzara, G.; Milioto, S.; Parisi, F. Coffee grounds as filler for pectin: Green composites with
competitive performances dependent on the UV irradiation. Carbohydr. Polym. 2017, 170, 198–205. [CrossRef]
14. Ciapponi, R.; Turri, S.; Levi, M. Mechanical reinforcement by microalgal biofiller in novel thermoplastic biocompounds from
plasticized gluten. Materials 2019, 12, 1476. [CrossRef]
15. Rasal, R.M.; Janorkar, A.V.; Hirt, D.E. Poly(lactic acid) modifications. Prog. Polym. Sci. 2010, 35, 338–356. [CrossRef]
16. Kumar Bajpai, P.; Singh, I.; Madaan, J. Development and characterization of PLA-based green composites: A review. J. Thermoplast.
Compos. Mater. 2014, 27, 52–81. [CrossRef]
17. Marimuthu, D.; Rajesh, K.; Ravikumar, S.M. Applications of CT/CAD/RPT in the futuristic development of orthopaedics and
fabrication of plate and screw material from natural fiber particle reinforced composites for humerus bone fixation—A future
drift. Malays. J. Educ. Technol. 2010, 10, 73–81.
18. Abdul Khalil, H.P.S.; Bhat, A.H.; Ireana Yusra, A.F. Green composites from sustainable cellulose nanofibrils: A review. Carbohydr.
Polym. 2012, 87, 963–979. [CrossRef]
19. Zhao, D.; Cai, X.; Shou, G.; Gu, Y.; Wang, P. Study on the preparation of bamboo plastic composite intend for additive
manufacturing. Key Eng. Mater. 2016, 667, 250–258. [CrossRef]
20. Tao, Y.; Wang, H.; Li, Z.; Li, P.; Shi, S.Q. Development and application of wood flour-filled polylactic acid composite filament for
3D printing. Materials 2017, 10, 339. [CrossRef] [PubMed]
21. Martikka, O.; Kärki, T.; Wu, Q. Mechanical properties of 3D-printed wood-plastic composites. Key Eng. Mater. 2018, 777,
499–507. [CrossRef]
22. Gkartzou, E.; Koumoulos, E.P.; Charitidis, C.A. Production and 3D printing processing of bio-based thermoplastic filament.
Manuf. Rev. 2017, 4, 1. [CrossRef]
23. Daver, F.; Lee, K.P.M.; Brandt, M.; Shanks, R. Cork–PLA composite filaments for fused deposition modelling. Compos. Sci. Technol.
2018, 168, 230–237. [CrossRef]
24. Mazzanti, V.; Malagutti, L.; Mollica, F. FDM 3D printing of polymers containing natural fillers: A review of their mechanical
properties. Polymers 2019, 11, 1094. [CrossRef] [PubMed]
25. López-López, A.; Davila-Vazquez, G.; León-Becerril, E.; Villegas-García, E.; Gallardo-Valdez, J. Tequila vinasses: Generation and
full scale treatment processes. Rev. Environ. Sci. Biotechnol. 2010, 9, 109–116. [CrossRef]
26. Consejo Regulador de Tequila. Available online: https://www.crt.org.mx/EstadisticasCRTweb/ (accessed on 1 February 2021).
27. Hulle, A.; Kadole, P.; Katkar, P. Agave Americana leaf fibers. Fibers 2015, 3, 64–75. [CrossRef]
28. Torres-Tello, E.V.; Robledo-Ortíz, J.R.; González-García, Y.; Pérez-Fonseca, A.A.; Jasso-Gastinel, C.F.; Mendizábal, E. Ef-
fect of agave fiber content in the thermal and mechanical properties of green composites based on polyhydroxybutyrate
or poly(hydroxybutyrate-co-hydroxyvalerate). Ind. Crops Prod. 2017, 99, 117–125. [CrossRef]
29. Cisneros-López, E.O.; Pérez-Fonseca, A.A.; González-García, Y.; Ramírez-Arreola, D.E.; González-Núñez, R.; Rodrigue, D.;
Robledo-Ortíz, J.R. Polylactic acid–agave fiber biocomposites produced by rotational molding: A comparative study with
compression molding. Adv. Polym. Technol. 2018, 37, 2528–2540. [CrossRef]
30. Pérez-Fonseca, A.A.; Gómez, C.; Dávila, H.; González-Núñez, R.; Robledo-Ortíz, J.R.; Vázquez-Lepe, M.O.; Herrera-Gómez, A.
Chitosan Supported onto Agave Fiber—Postconsumer HDPE Composites for Cr(VI) Adsorption. Ind. Eng. Chem. Res. 2012, 51,
5939–5946. [CrossRef]
31. User’s Guide TRIOS Software; TA Instruments: New Castle, DE, USA, 2018.
32. Zhao, H.; Cui, Z.; Sun, X.; Turng, L.S.; Peng, X. Morphology and properties of injection molded solid and microcellular polylactic
acid/polyhydroxybutyrate-valerate (PLA/PHBV) blends. Ind. Eng. Chem. Res. 2013, 52, 2569–2581. [CrossRef]
33. SketchUp Support. Available online: https://help.sketchup.com/en/sketchup/sketchup (accessed on 2 June 2021).
34. Repetier-Host Software documentation. Available online: https://www.repetier.com/documentation/repetier-host (accessed on
2 June 2021).
35. Alam, A.K.M.M.; Mina, M.F.; Beg, M.D.H.; Mamun, A.A.; Bledzki, A.K.; Shubhra, Q.T.H. Thermo-mechanical and morphological
properties of short natural fiber reinforced poly (lactic acid) biocomposite: Effect of fiber treatment. Fibers Polym. 2014, 15,
1303–1309. [CrossRef]
36. User’s Guide STATGRAPHICS Centurion XV; StatPoint Inc: The Plains, VA, USA, 2005.
37. Vaxman, A.; Narkis, M.; Siegmann, A.; Kenig, S. Short-fiber-reinforced thermoplastics. Part III: Effect of fiber length on rheological
properties and fiber orientation. Polym. Compos. 1989, 10, 454–462. [CrossRef]
38. Yang, Z.; Feng, X.; Bi, Y.; Zhou, Z.; Yue, J.; Xu, M. Bleached extruder chemi-mechanical pulp fiber-PLA composites: Comparison
of mechanical, thermal, and rheological properties with those of wood flour-PLA bio-composites. J. Appl. Polym. Sci. 2016, 133,
1–9. [CrossRef]
39. De Meo, A.; De Santis, F.; Pantani, R. Effects of rapid cavity temperature variations on the crystallinity of PLA. In Proceedings of
the AIP Conference Proceedings, Cesme-Izmir, Turkey, 26–30 May 2019; American Institute of Physics Inc.: College Park, MD,
USA, 2020; Volume 2205, p. 020016.
40. Pérez-Fonseca, A.A.; Robledo-Ortíz, J.R.; González-Núñez, R.; Rodrigue, D. Effect of thermal annealing on the mechanical and
thermal properties of polylactic acid-cellulosic fiber biocomposites. J. Appl. Polym. Sci. 2016, 133, 1–9. [CrossRef]
41. Teixeira, E.d.M.; Curvelo, A.A.S.; Corrêa, A.C.; Marconcini, J.M.; Glenn, G.M.; Mattoso, L.H.C. Properties of thermoplastic starch
from cassava bagasse and cassava starch and their blends with poly (lactic acid). Ind. Crops Prod. 2012, 37, 61–68. [CrossRef]
Materials 2021, 14, 3111 16 of 16

42. Osman, M.A.; Atia, M.R.A. Investigation of ABS-rice straw composite feedstock filament for FDM. Rapid Prototyp. J. 2018, 24,
1067–1075. [CrossRef]
43. Smith, W.C.; Dean, R.W. Structural characteristics of fused deposition modeling polycarbonate material. Polym. Test. 2013, 32,
1306–1312. [CrossRef]
44. Cole, D.P.; Riddick, J.C.; Iftekhar Jaim, H.M.; Strawhecker, K.E.; Zander, N.E. Interfacial mechanical behavior of 3D printed ABS. J.
Appl. Polym. Sci. 2016, 133, 1–12. [CrossRef]
45. Zhang, W.; Wu, A.S.; Sun, J.; Quan, Z.; Gu, B.; Sun, B.; Cotton, C.; Heider, D.; Chou, T.W. Characterization of residual stress and
deformation in additively manufactured ABS polymer and composite specimens. Compos. Sci. Technol. 2017, 150, 102–110. [CrossRef]
46. Huda, M.S.; Drzal, L.T.; Mohanty, A.K.; Misra, M. Effect of fiber surface-treatments on the properties of laminated biocomposites
from poly(lactic acid) (PLA) and kenaf fibers. Compos. Sci. Technol. 2008, 68, 424–432. [CrossRef]
47. Ning, F.; Cong, W.; Qiu, J.; Wei, J.; Wang, S. Additive manufacturing of carbon fiber reinforced thermoplastic composites using
fused deposition modeling. Compos. Part B Eng. 2015, 80, 369–378. [CrossRef]
48. Mohanty, A.K.; Misra, M.; Drzal, L.T. Sustainable bio-composites from renewable resources: Opportunities and challenges in the
green materials world. J. Polym. Environ. 2002, 10, 19–26. [CrossRef]
49. Pérez-Fonseca, A.A.; Robledo-Ortíz, J.R.; Moscoso-Sánchez, F.J.; Rodrigue, D.; González-Núñez, R. Injection molded self-hybrid
composites based on polypropylene and natural fibers. Polym. Compos. 2014, 35, 1798–1806. [CrossRef]
50. Yew, G.H.; Mohd Yusof, A.M.; Mohd Ishak, Z.A.; Ishiaku, U.S. Water absorption and enzymatic degradation of poly(lactic acid)/rice
starch composites. Polym. Degrad. Stab. 2005, 90, 488–500. [CrossRef]
51. Vicente, C.M.S.; Fernandes, J.; Reis, L.; De Deus, A.M.; Vaz, M.F.; Leite, M. Effect of protective coatings on the water absorption
and mechanical properties of 3D printed PLA. Frat. Integrita Strutt. 2019, 13, 748–756. [CrossRef]
52. Taib, R.M.; Ramarad, S.; Ishak, Z.A.M.; Todo, M. Water absorption and tensile properties of kenaf bast fiber-plasticized
poly(lactic acid) biocomposites. In Proceedings of the Polymer Proceeding Society 24th Annual Meeting, Solerno, Italy,
15–19 June 2008; pp. 2–5.
53. Pérez-Fonseca, A.A.; Arellano, M.; Rodrigue, D.; González-Núñez, R.; Robledo-Ortíz, J.R. Effect of coupling agent content and
water absorption on the mechanical properties of coir-agave fibers reinforced polyethylene hybrid composites. Polym. Compos.
2016, 37, 3015–3024. [CrossRef]
54. Rajesh, G.; Prasad, A.R.; Gupta, A. Mechanical and degradation properties of successive alkali treated completely biodegradable
sisal fiber reinforced poly lactic acid composites. J. Reinf. Plast. Compos. 2015, 34, 951–961. [CrossRef]
55. Le Duigou, A.; Castro, M.; Bevan, R.; Martin, N. 3D printing of wood fibre biocomposites: From mechanical to actuation
functionality. Mater. Des. 2016, 96, 106–114. [CrossRef]
56. Cisneros-López, E.O.; Anzaldo, J.; Fuentes-Talavera, F.J.; González-Núñez, R.; Robledo-Ortíz, J.R.; Rodrigue, D. Effect of agave
fiber surface treatment on the properties of polyethylene composites produced by dry-blending and compression molding. Polym.
Compos. 2017, 38, 96–104. [CrossRef]
57. Liu, H.; He, H.; Peng, X.; Huang, B.; Li, J. Three-dimensional printing of poly(lactic acid) bio-based composites with sugarcane
bagasse fiber: Effect of printing orientation on tensile performance. Polym. Adv. Technol. 2019, 30, 910–922. [CrossRef]
58. Johari, A.P.; Mohanty, S.; Kurmvanshi, S.K.; Nayak, S.K. Influence of different treated cellulose fibers on the mechanical and
thermal properties of poly(lactic acid). ACS Sustain. Chem. Eng. 2016, 4, 1619–1629. [CrossRef]
59. Dawoud, M.; Taha, I.; Ebeid, S.J. Mechanical behaviour of ABS: An experimental study using FDM and injection moulding
techniques. J. Manuf. Process. 2016, 21, 39–45. [CrossRef]
60. Rezayat, H.; Zhou, W.; Siriruk, A.; Penumadu, D.; Babu, S. Structure-mechanical property relationship in fused deposition
modelling. Mater. Sci. Technol. 2015, 31, 895–903. [CrossRef]
61. Es-Said, O.S.; Foyos, J.; Noorani, R.; Mendelson, M.; Marloth, R.; Pregger, B.A. Effect of Layer Orientation on Mechanical
Properties of Rapid Prototyped Samples. Mater. Manuf. Process. 2000, 15, 107–122. [CrossRef]
62. Yussuf, A.A.; Massoumi, I.; Hassan, A. Comparison of polylactic acid/kenaf and polylactic acid/rise husk composites: The influence
of the natural fibers on the mechanical, thermal and biodegradability properties. J. Polym. Environ. 2010, 18, 422–429. [CrossRef]
63. Iovino, R.; Zullo, R.; Rao, M.A.; Cassar, L.; Gianfreda, L. Biodegradation of poly(lactic acid)/starch/coir biocomposites under
controlled composting conditions. Polym. Degrad. Stab. 2008, 93, 147–157. [CrossRef]
64. Dong, Y.; Ghataura, A.; Takagi, H.; Haroosh, H.J.; Nakagaito, A.N.; Lau, K.T. Polylactic acid (PLA) biocomposites reinforced with
coir fibres: Evaluation of mechanical performance and multifunctional properties. Compos. Part A Appl. Sci. Manuf. 2014, 63,
76–84. [CrossRef]