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Effect of Nanometric Particles of Bentonite on the Mechanical Properties of a

Thermoset Polymeric Matrix Reinforced with Hemp Fibers

Article  in  Composite Polymers · March 2023

DOI: 10.3390/polym15061571

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 polymers
Article
Effect of Nanometric Particles of Bentonite on the Mechanical
Properties of a Thermoset Polymeric Matrix Reinforced with
Hemp Fibers
Meylí Valin Fernández 1, * , María José Ahumada González 2 , Rolando Briones Oyanadel 2 ,
José Luis Valin Rivera 2 , Angel Rodríguez Soto 2 , Alvaro González Ortega 2 , Cristobal Galleguillos Ketterer 2 ,
Alexander Alfonso Alvarez 3 , Francisco Rolando Valenzuela Diaz 4 and Gilberto García del Pino 5

1 Department of Mechanical Engineering (DIM), Faculty of Engineering (FI), University of Concepción,

Concepción 4030000, Chile
2 Escuela de Ingeniería Mecánica, Pontificia Universidad Católica de Valparaíso, Valparaíso 2340025, Chile
3 Departamento de Ingeniería Mecánica, Facultad de Ingeniería, Universidad de la Serena,
La Serena 1720010, Chile
4 Departamento de Engenharia Metalúrgica e de Materiais, Escola Politécnica,
Universidade de São Paulo (USP), São Paulo 05508-220, Brazil
5 College of Technology, State University of Amazonas, Manaus 69850-000, Brazil
* Correspondence: [email protected]

Abstract: The influence of the addition of bentonite nanoparticles on the tensile and flexural strength
of a thermosetting polymer matrix composite material reinforced with hemp fibers was de-terminated.
All composites were manufactured with 5% of bentonite in the polymer mass–weight ratios and
10 to 45 wt% of fibers with a step of 5%. For mechanical characterization, tensile and flexural tests
Citation: Fernández, M.V.; were performed: scanning electron microscopy and energy-dispersive X-ray spectroscopy analyses
González, M.J.A.; Oyanadel, R.B.; were carried out. The tensile strength of the samples containing bentonite compared to the polymer
Rivera, J.L.V.; Soto, A.R.; samples with the fiber addition was affected for all fiber addition percentages, except for 35% while
Ortega, A.G.; Ketterer, C.G.; the flexural resistance improved with the addition of bentonite in the percentages of 20, 30, 35, and
Alvarez, A.A.; Diaz, F.R.V.; 45% of fiber addition. With the addition of bentonite, the maximum values of tensile and flexural
García del Pino, G. Effect of
strength were both obtained for the 35% addition of fibers, with values of 34.28 MPa and 98.04 MPa,
Nanometric Particles of Bentonite on
respectively. The presence of bentonite favored the rigidity of the material to traction and bending,
the Mechanical Properties of a
which was reflected through an increase in the elastic modulus compared to the composite that only
Thermoset Polymeric Matrix
had fiber. The maximum values obtained were 9065 MPa in tension and 8453 MPa in flexion for the
Reinforced with Hemp Fibers.
Polymers 2023, 15, 1571. https://
40% and 35% of addition of fiber, respectively. Microscopy showed a good distribution of fibers in the
doi.org/10.3390/polym15061571 matrix, the absence of internal porosities, and a good interaction between matrix and reinforcement.

Academic Editors: María del

Keywords: vegetable fiber; bentonite; polymer composite; mechanical properties
Carmen Serna Moreno and
Sergio Horta Muñoz

Received: 28 February 2023

Revised: 18 March 2023 1. Introduction
Accepted: 20 March 2023 Reinforced polymer composites are the base of many modern products, since due to the
Published: 22 March 2023
combination of properties, they report a better mechanical and economical response [1–3].
The applications of the composites are diverse in different areas, marine [4], automotive [5],
civil infrastructure [6], and biomedical [7]. With the level of industrialization and pollution
Copyright: © 2023 by the authors.
existing worldwide, it is necessary to think about materials that cause low environment con-
Licensee MDPI, Basel, Switzerland. tamination. One option is to replace conventional synthetic reinforcements with vegetable
This article is an open access article fiber reinforcements, which in addition to not interfering with the environment, have a
distributed under the terms and lower manufacturing cost, low weight, biodegradable, and good mechanical properties [8].
conditions of the Creative Commons Suriyaprakash et al. presented a mechanical characterization of hybrid epoxy com-
Attribution (CC BY) license (https:// posites reinforced with ramie particles, hemp fibers, and coconut shell, laminated by
creativecommons.org/licenses/by/ compression molding where the best results in mechanical properties were found in the
4.0/). compositions with higher percentages of hemp (14%), with values of 71.5 MPa for the

Polymers 2023, 15, 1571. https://doi.org/10.3390/polym15061571 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 1571 2 of 14

tensile strength and 104.7 MPa for the flexural strength [9]. Jute fiber, on the other hand,
was studied as reinforcement by a vacuum-assisted epoxy resin infusion with different
fiber orientations by Hossain et al. [10], with mechanical characterization by three-point
tensile and flexural tests, showing results of higher strength in the longitudinal direction
than in the transverse, with a value of 39.10 MPa for a 0–90 laminate configuration. A
combination of unsaturated polyester resins such as a matrix with sisal, nacha, and e-glass
fiber as reinforcements were used by Miliket et al. [11] as a hybrid composite for wind
turbine blade applications using manual lamination, with a contribution to the tensile
strength of 220.12 MPa (10 wt% of glass, 10 wt% of nacha, and 20 wt% sisal), compressive
strength of 308.55 MPa (10 wt% of glass, 5 wt% of nacha, and 15 wt% sisal), and flexural
strength of 210.43 MPa (10 wt% of glass, 10 wt% of nacha, and 20 wt% sisal). Otherwise,
Mahesh et al. [12] studied the potential of a hybrid composite of pure polypropylene, sisal
fibers, ramie fibers, and maleic grafted anhydride (MagH) developed by the melt blending
method with the aid of twin-screw extrusion molding with the maximum value of the
tensile strength of 41.2 MPa (87 wt% of polypropylene, 3 wt% of MagH, 5 wt% of sisal, and
5 wt% of ramie fibers) and flexural strength of 60.5 MPa (67 wt% of polypropylene, 3 wt%
of MagH, 15 wt% of sisal, and 15 wt% of ramie fibers). Banana, coconut, jute, and cotton
fibers as reinforcement at different weight ratios with a matrix of polyethylene were also
studied by Paladugu et al. [13], with the maximum value of the tensile strength of 55 MPa
(70 wt% of matrix, 5 wt% of jute, 5 wt% of banana, and 20 wt% of coconut) and a flexural
strength of 1700 MPa (70 wt% of matrix, 5 wt% of cotton, 18 wt% of banana, and 7 wt%
of coconut).
In Chile, a plant species that is of interest is hemp (Cannabis sativa), whose cultivation
in the country is used mostly in the textile industry today. Hemp fibers, as a reinforcement
of polymeric matrix composite materials, have reported improvements in mechanical
properties such as longitudinal and transverse Young’s modulus as well as the shear
Young’s modulus [14]. On the other hand, Panaitescu et al. [15] exposed in their work
a polymer matrix composite reinforced with hemp fiber at lengths of 1, 2.5, and 4 mm
obtained through an extrusion process where the maximum value of resistance to tensile
strength was 39 MPa (polypropylene, 5 wt% of maleic anhydride grafted polypropylene,
15 wt% of Kraton 1652 G, 30 wt% of hemp fiber with 4 mm of length) and a tensile Young’s
modulus of 3000 MPa. Neves et al. [16] conducted a study where they manufactured two
composites: one with a base of epoxy and hemp fibers and the other with a base of polyester
resin and hemp fibers. The flexural strength maximum value of 76.69 MPa was obtained
for the 30 wt% of hemp fiber with epoxy, compared with the value of 50.75 MPa for the
hemp fiber and polyester resin. For the tensile strength, the maximum value of 50.46 MPa
was also obtained for the 30 wt% of hemp fiber with epoxy compared with the value of
31.46 MPa for hemp fiber and polyester resin.
Another way to modify the properties of the resin is by adding particles, which
depends on the configuration and interfacial interaction of the latter with the resin [14].
Bentonite, for example, is a type of clay that has good water absorption and compressive
strength behavior [16,17]; good sound absorption capacity in combination with natural
fibers [18], or impermeability under high concentration of heavy metal solution [19]. Its
contribution in the improvement in mechanical properties has been reflected by Arash
et al. [20], in combination with polylactic acid polymer and thermoplastic polyurethane
where the Young’s modulus in tension was 1650 MPa for a 3 wt% of bentonite particles
compared with the 15,545 MPa of the thermoplastic polyurethane; in combination with
epoxy resin as presented by Mahadeva et al., where the tensile and compressive strength
were 18 MPa (7 wt% of nanoparticles of bentonite) and 190 MPa (7 wt% of nanoparticles of
bentonite) compared with 14 MPa and 100 MPa of the epoxy resin only [21]; in combination
with polystyrene where the alignment of the clay particles into the polymer matrix reduced
the resistance compared to the composite for a random orientation of the clay particles [22].
In the present work, the influence of nanometric bentonite particles in the mechanical
properties of a thermoset polymer matrix composite material reinforced with hemp fibers
Polymers 2023, 15, 1571 3 of 14

was carried out. In the present work, the influence of nanometric bentonite particles on the
mechanical properties of a thermoset polymer matrix composite material reinforced with
hemp fibers was studied. The novelty is reflected through the following points:
 The literature consulted thus far does not report work with these materials and the
manufacturing method proposed here.
 It was possible to verify that nanometric-sized bentonite particles guarantee a better
interaction with the matrix.
 The use of nanometric bentonite particles improves the stiffness of the compound by
increasing its tensile and flexural elastic modulus.

2. Materials and Methods

2.1. Materials
An orthophthalic unsaturated polyester polymer (CRISTALÁN 859) was selected
and its properties are shown in Table 1. Methyl ethyl ketone peroxide (MEK) (with 9%
active O2 ) and cobalt octoate (6% Co) were used as a catalyst and as an accelerator for
hardening at room temperature, respectively, manufactured by Andercol S.A., Colombia. It
was determined that the best proportion of the elements for the 2% catalyst was between
0.05% and 0.1% of the accelerator (based on the mass of resin used for each plate).

Table 1. The properties of Cristalán 859.

Properties Typical Values

APHA Color 80 maximum
Acid number 32 maximum
Brookfield viscosity (cps), 25 ◦ C (needle 2, 20 r.p.m., 1 min). 500–700
Solid (%) 64–66
Gel time at 25 ◦ C, min. 7–10
Reactivity:
Exotherm temperature, ◦ C. 140–160
Exotherm temperature, min. 17–25
Stability at 60 ◦ C, horas. 168 minimum

The hemp fibers used as reinforcement were obtained from commercial braided hemp,
which was separated into strands. The bentonite used as the ceramic filler was Rheotix VP
bentonite of the calcium type provided by the University of Sao Paulo (USP).

2.2. Fabrication of the Composite

The fiber length was determined according to the critical length criterion, as presented
by Equation (1) [23].
σf d f
lc = (1)
2τc
where σf is the maximum stress that the fiber resists; df is the fiber diameter; τ c is the shear
strength of the matrix; and lc is the critical length.
First, the diameter of the fibers was measured, and for this purpose, a Carl Zeiss Jena
optical microscope at 100× coupled to a computer was used. Subsequently, the maximum
stress that the fiber resists and the shear stress were determined using a universal testing
machine model WDW-200E from the TIME Group Inc., with a maximum load of 200 kN
and a precision of ±0.0001 kN for a total of 20 fibers. With the results obtained, the fiber
diameter (0.016 mm), the ultimate stress (260.4 MPa), and the shear stress of the matrix
(4.3 MPa), the length value obtained was 4.8 mm, so it was decided to cut the fiber with a
length of 25 mm.
For the manufacture of the composite material, three box-type molds of SAE 1045 material
were used, stacked one on top of the other, which allowed for the manufacture of several
plates at the same time by the molding compression method, making it possible to obtain
composite plates with the dimensions of 250 × 156 × 3 (mm).
Polymers 2023, 15, 1571 4 of 14

For the tensile strength analysis, only fiber boards were manufactured, in percentages
of weight ratios from 10 to 45 wt% of hemp fiber in five steps with random orientation in
proportion to the mass of the polymer. For both the analyses of the tensile and flexural tests,
plates with the same proportions above-mentioned were prepared with the addition of
bentonite, which was set at a value of 5 wt% in proportion to the mass of the polymer. The
bentonite nanometric particles were fixed to 5 wt% based on the polymer mass according
to the results of Fernández et al. [23]. All of the plates were made by mixing the materials
manually and once incorporated into the molds, they were covered and taken to a press
that applied a load of 4 tons for a period of 24 h. Once removed from the molds, they were
stored and protected from light for 25 days to comply with the post-curing process.
Polymers 2023, 15, x FOR PEER REVIEW 5 of 14
2.3. Mechanical Characterization
The mechanical characterization was carried out through tensile and bending tests.
The tensile
H40tests were carried out60following the ASTM D638-14
40 standard in a -universal
testing machine
H45 model WDW-200E 55 from the TIME Group Inc.,
45 with a maximum - load of
200 kN and a precision of ±0.0001 kN; a model MC extensometer and a precision of 0.001
B5H10 85 10 5
were used under a monotonic load over time and with a strain rate of 1 mm/min, as
B5H15 80 15 5
presented in Figure 1a. To obtain the geometry indicated by the standard, the plates were
B5H20 75 20
cut using a BCL 1309X model laser from the BODOR company with an intensity of 5 10 (mA)
B5H25 70 25 5 to the
and a cutting speed of 14 mm/s at a distance of 3 mm from the nozzle of the machine
surfaceB5H30 65 the rectangles were obtained
of the plate to be cut. Once 30 5 of the
to obtain the neck
B5H35 60 35
test tubes, a model CAMM-3 PNC-2500 milling cutter from the company Roland 5 Digital
Group B5H40 55 a 6 mm diameter milling
was used. For this operation, 40 cutter with a rotation
5 speed
of 6000B5H45
rpm and a linear speed of 5014 mm/s was used, with 45 successive passes at
5 3.6 mm
from one to the other. The dimensions of the tensile specimen were 165 × 19 × 3 (mm).

(a) (b)
Figure 1.
Figure 1. Experimental tests: (a)
Experimental tests: (a) tensile
tensile test
test and
and (b)
(b) flexural test.
flexural test.

An analysis
The bendingwastestscarried out byout
were carried scanning electron
following microscopy
the ASTM (SEM)
D7264-15 using ZEISS
standard in the
EVO MA10 equipment to obtain information on the internal structure
universal machine described above, with the same extensometer and using the same of the hempspeed,
stem
such three
with as thesupport
thickness, cell wall
points, area, morphology,
as presented in Figureand
1b. inThethespecimens,
case of the being
fractures, observe
rectangular,
the interface
were between
cut by laser, withthe
the polymer and the fiber.
same equipment Thethe
used for microscopies
manufacture inofthe fractures
tensile of the
specimens
material
and were carried
maintaining out incutting
the same tensileparameters.
specimens, and
Theas it is a non-conductive
dimensions of the bendingmaterial, they
specimen
were 96
were metallized
× 13 × 3with
(mm).a thin
The layer of gold. used for the samples is presented in the Table 2.
nomenclature
On the other hand, energy-dispersive X-ray spectroscopy (EDS) analysis was carried
out on the bentonite to obtain its characterization, both in terms of the morphology and
chemical composition. For this, a Hitachi SU3500 model scanning electron microscope was
used with an XFlash 410-M.

3. Results and Discussion

Polymers 2023, 15, 1571 5 of 14

Table 2. Nomenclature of the samples.

Specimen Polyester Polymer (P) [%] Hemp Fiber (H) [%] Bentonite (B) [%]
P 100 - -
H10 90 10 -
H15 85 15 -
H20 80 20 -
H25 75 25 -
H30 70 30 -
H35 65 35 -
H40 60 40 -
H45 55 45 -
B5H10 85 10 5
B5H15 80 15 5
B5H20 75 20 5
B5H25 70 25 5
B5H30 65 30 5
B5H35 60 35 5
B5H40 55 40 5
B5H45 50 45 5

An analysis was carried out by scanning electron microscopy (SEM) using ZEISS
EVO MA10 equipment to obtain information on the internal structure of the hemp stem
such as the thickness, cell wall area, morphology, and in the case of the fractures, observe
the interface between the polymer and the fiber. The microscopies in the fractures of the
material were carried out in tensile specimens, and as it is a non-conductive material, they
were metallized with a thin layer of gold.
On the other hand, energy-dispersive X-ray spectroscopy (EDS) analysis was carried
out on the bentonite to obtain its characterization, both in terms of the morphology and
chemical composition. For this, a Hitachi SU3500 model scanning electron microscope was
used with an XFlash 410-M.

3. Results and Discussion

3.1. Energy-Dispersive X-ray Spectroscopy (EDS)
Polymers 2023, 15, x FOR PEER REVIEW 6 of 14
For the EDS analysis, three samples of dry untreated bentonite were used. Figure 2
shows the diffractogram of a bentonite sample, and Table 3 shows the chemical composition.

Figure 2.
Figure 2. EDS analysis.
analysis.

Table 3. Bentonite chemical composition.

Mass Mass Norm. Atom Abs. Error [%] Real. Error [%]
Element At. No. Netto
[%] [%] [%] (1 Sigma) (1 Sigma)
Polymers 2023, 15, 1571 6 of 14

Table 3. Bentonite chemical composition.

Mass Mass Norm. Atom Abs. Error [%] Real. Error [%]
Element At. No. Netto
[%] [%] [%] (1 Sigma) (1 Sigma)
Oxygen 8 7219 40.28 45.00 47.12 5.95 14.77
Carbon 6 1609 22.90 25.59 35.69 4.60 20.08
Silicon 14 18,146 15.47 17.28 10.31 0.70 4.55
Aluminum 13 6830 7.04 7.87 4.89 0.38 5.46
Magnesium 12 886 1.12 1.25 0.86 0.11 9.61
Iron 26 366 1.06 1.19 0.36 0.09 8.59
Potassium 19 792 0.96 1.08 0.46 0.07 7.69
Calcium 20 459 0.66 0.74 0.31 0.06 9.76
Sum. 89.50 100.00 100.00

Table 3 shows that the sample contained 0.66% calcium, which is why it is classified
as a calcium-type bentonite. Other important components found were carbon, silicon,
and aluminum.

3.2. Scanning Electron Microscopy

From the SEM analysis of the bentonite samples, the images presented in Figure 3
were obtained. It can be seen in Figure 3a that the size of the grains varied in the sample,
perceiving in the center of this a grain of greater dimension with respect to those that
surrounded them. Figure 3b shows that the irregular surface has features that are suitable
for the interface (adhesion) between the polyester resin and the bentonite, as presented by
Seghar and Azem [24]. The variation in the particle size ensures better interaction with the
polymer matrix, where smaller grains provide better results when the material is subjected
Polymers 2023, 15, x FOR PEER REVIEW 7 ofthe
to traction due to the increase in the surface area of the particle size, which increases 14

rate of attraction of particles in the bentonite to polyester polymer [25].

(a) (b)
Figure 3. Scanning electron microscopy (SEM) in a bentonite sample: (a) variability of grain size; (b)
Figure 3. Scanning electron microscopy (SEM) in a bentonite sample: (a) variability of grain size;
surface appearance.
(b) surface appearance.

Optical
The grainsmicroscopies of thea shape
have, in general, cross section of hemptostems
with a tendency were This
sphericity. obtained
favorswhere the
the active
shape of the fibers, the thickness of the cell wall, and its area can be appreciated.
surface (particle–matrix interface) and slows down the propagation of cracks (decreased These
factors influence
stresses). However, theitstrength
has beenoffound
the fibers and their structural
that elongated functionshape”,
shapes, a “needle as reinforcements
offer better
in the composite. Figure
mechanical properties [26,27].4a shows the hue of the stem and the softer substance called the
reed Optical
characteristics that contribute
microscopies of the crossto thermal and
section of acoustic
hemp insulation,
stems while where
were obtained Figure the
4b
depicts
shape ofthethecells thatthe
fibers, make up the of
thickness vegetable
the cell fiber.
wall, and its area can be appreciated. These
factors influence the strength of the fibers and their structural function as reinforcements in
 (a) (b)
Figure 3. Scanning electron microscopy (SEM) in a bentonite sample: (a) variability of grain size; (b)
surface appearance.

Polymers 2023, 15, 1571 Optical microscopies of the cross section of hemp stems were obtained where the
7 of 14
shape of the fibers, the thickness of the cell wall, and its area can be appreciated. These
factors influence the strength of the fibers and their structural function as reinforcements
in
thethe composite.
composite. Figure
Figure 4a shows
4a shows the the
huehue of the
of the stemstem
and and the softer
the softer substance
substance called
called the
the reed
reed characteristics that contribute to thermal and acoustic insulation, while Figure
characteristics that contribute to thermal and acoustic insulation, while Figure 4b depicts 4b
depicts
the cellsthe cells
that makethat
upmake up the vegetable
the vegetable fiber. fiber.

(a) (b)
Figure 4. Optical microscopy in a sample of hemp: (a) cross section in the stem, 40×; (b) cells that
Figure 4. Optical microscopy in a sample of hemp: (a) cross section in the stem, 40×; (b) cells that
make up the fiber, 400×.
make up the fiber, 400×.

In natural fibers,
In natural fibers,there
thereis,
is,iningeneral,
general,disparity
disparityinin the
the shape
shape andand size
size of the
of the cross
cross sec-
section,
tion, however, in Table 4, both the thickness of the wall of the fibers and the area
however, in Table 4, both the thickness of the wall of the fibers and the area of said wall in of said
wall
narrowin narrow
marginsmargins
could becould be observed.
observed.

Table 4. Thickness and area of the cell wall of hemp.

Specie Sample Cell Wall Thickness [µm] Cell Wall Area [µm2 ]
1 1.9 49.5
2 2.0 55.9
Hemp 3 2.1 54
4 1.9 55
5 2.1 53
Average 2.0 53.5

Figure 5 shows the diameter of the fiber, which can also be perceived as having a
rough surface; this condition improves the union between the polymer and the fiber.
Additionally, once the tensile tests were carried out, an analysis of the fracture zones
was executed. Figure 6 shows the breakage areas of the test tubes identifying the separa-
tion of the fibers from the matrix, breakage of the fibers, and breakage of the polymeric
matrix. We also observed the topography of each fiber, and the irregularities that favor
the mechanical union of the interface. The presence of air bubbles or the inclusion of other
defects that affect the resistance of the compound was not detected.
 4 1.9 55
5 2.1 53
Average 2.0 53.5

Polymers 2023, 15, 1571 Figure 5 shows the diameter of the fiber, which can also be perceived 8as
of 14
having a
rough surface; this condition improves the union between the polymer and the fiber.

(a) (b)
Figure 5. Scanning electron microscopy (SEM) in the hemp sample: (a) bundle of fibers, 1000×; (b)
measurements of a fiber, 10,000×.

Additionally, once the tensile tests were carried out, an analysis of the fracture zones
was executed. Figure 6 shows the breakage areas of the test tubes identifying the separa-
tion of the fibers from the matrix, breakage of the fibers, and breakage of the polymeric
(a) We also observed the topography of each fiber,
matrix. (b) and the irregularities that favor
theFigure
Figuremechanical
5. Scanning union
5. Scanning of the
electron
electron interface.(SEM)
microscopy
microscopy The presence
(SEM) inthe
in ofsample:
thehemp
hemp air bubbles
sample:
(a) (a)or the
of inclusion
bundle
bundle of fibers,
fibers, 1000×of
; other(b)
1000×;
defects that affect
measurements the
of a fiber,
(b) measurements of resistance
10,000×of
10,000×.
a fiber, . the compound was not detected.

Additionally, once the tensile tests were carried out, an analysis of the fracture zones
was executed. Figure 6 shows the breakage areas of the test tubes identifying the separa-
tion of the fibers from the matrix, breakage of the fibers, and breakage of the polymeric
matrix. We also observed the topography of each fiber, and the irregularities that favor
the mechanical union of the interface. The presence of air bubbles or the inclusion of other
defects that affect the resistance of the compound was not detected.

(a) (b)
Figure 6. Scanning
Figure 6. Scanningelectron
electronmicroscopy (SEM)inin
microscopy (SEM) the
the tensile
tensile testtest specimen
specimen fracture
fracture zone: zone: (a) sample
(a) sample
PPH25, 146×; (b) sample PPH20, 200×.
PPH25, 146×; (b) sample PPH20, 200×.

3.3. Tensile Strength

The tensile test was carried out on a quantity of not less than five test pieces of each
of the percentages indicated above. The tensile strength values for the samples with the
addition of fiber only and the samples with the addition of fiber and bentonite are shown
(a) (b) of the elastic module are
in Figures 7a and 7b, respectively. In Figure 7c,d, the values
presented for the samples with the addition of fiber only and the samples with the addition
Figure 6. Scanning
of fiber electronrespectively.
and bentonite, microscopy (SEM) in the tensile test specimen fracture zone: (a) sample
PPH25, 146×; (b) sample PPH20, 200×.
 3.3. Tensile Strength
The tensile test was carried out on a quantity of not less than five test pieces of each
of the percentages indicated above. The tensile strength values for the samples with the
addition of fiber only and the samples with the addition of fiber and bentonite are shown
Polymers 2023, 15, 1571 in Figure 7a and Figure 7b, respectively. In Figure 7c,d, the values of the elastic module
9 of 14
are presented for the samples with the addition of fiber only and the samples with the
addition of fiber and bentonite, respectively.

(a) (b)

(c) (d)
Figure 7. Tensile test results: (a) tensile strength of samples with addition of fibers only; (b) tensile
Figure 7. Tensile test results: (a) tensile strength of samples with addition of fibers only; (b) tensile
strength of samples with addition of fibers and bentonite; (c) elastic module of samples with addi-
strength of samples with addition of fibers and bentonite; (c) elastic module of samples with addition
tion of fibers only; (d) elastic module of samples with addition of fibers and bentonite.
of fibers only; (d) elastic module of samples with addition of fibers and bentonite.
The specimens without
The specimens withoutfibers
fibersbehaved
behaved like
like a brittle
a brittle material,
material, the stress
the stress grewgrew con-
constantly
stantly up to the point of fracture, and there was no point at which
up to the point of fracture, and there was no point at which the slope changes, differentiating the slope changes,
differentiating
between the elastic between and the elastic
plastic andthere
zones; plasticwas zones;
only anthere was zone.
elastic only an Theelastic
tensile zone. The
strength
tensile strength was the same as the rupture stress and the dispersion
was the same as the rupture stress and the dispersion was low. For the rest of the samples, was low. For the
rest of the samples, a certain degree of curvature was observed
a certain degree of curvature was observed due to the influence of the reinforcement due to the influence of the
reinforcement
(lignocellulosic(lignocellulosic fibers, with
fibers, with a viscoelastic a viscoelastic
behavior), but thebehavior),
yield pointbut could thenot yield point
be clearly
could
defined; however, by applying the 0.2% criterion, it was verified that there was no point that
not be clearly defined; however, by applying the 0.2% criterion, it was verified that
there
dividedwasthenoelastic
point and that plastic
divided the elastic
behavior, so and plastic behavior,
the material presentedsoonly
the material
the elasticpresented
zone. As
only the elastic of
the percentage zone.
fiberAs the percentage
increases, of fiber
the tensile increases,
strength theup
increases tensile
to 30strength
wt% of fiber increases
addition,up
to 30 wt% of fiber addition, and then began to decrease. This is a
and then began to decrease. This is a trend in fiber-reinforced polymer matrix composite trend in fiber-reinforced
polymer
materials,matrix
and it is composite materials,
justified because and
there is aitlimit
is justified because
to the amount of there
fibers is thata limit to the
can begin to
amount
optimally of cohere
fibers that the can begin
matrix; to optimally
when this limitcohere the matrix;
is exceeded, wheninthis
a decline thelimit is exceeded,
properties of the
amaterial
decline occurs,
in the properties
as presented of by
theVallejos
materialetoccurs,
al. [28] as
and presented
Rodriguez byetVallejos
al. [29].et al. [28] and
Rodriguez et al. [29].
For the specimens with the addition of fibers and bentonite, the tensile strength
For theinspecimens
decreased with the except
all of the samples, addition forofB5H5,
fibers which
and bentonite,
presented the antensile
increase strength de-
of 26.96%
creased in all to
with respect of sample
the samples,
H5, asexcept
can befor B5H5,
seen which7a,b.
in Figure presented an increase
This decrease of 26.96%
in tensile with
strength
due to the presence of bentonite may be due to the agglomerations of the particles within
the matrix. Small aggregates that form act as stress concentrators, acting as failure initiators.
The increase in the tensile strength presented by B5H5 could be attributed to the rigidity of
the filler particles. A similar behavior was reported by Sarkar et al. [27], where resistance
presents a turning point in their results.
Polymers 2023, 15, 1571 10 of 14

By also comparing the results between the compound with and without bentonite,
an increase in the dispersion of the values was found. This can be proven by the random
distribution of this within the matrix, which can generate a different mechanical response
for each sample, and a similar behavior was observed by Ollier et al. [28].
Table 5 shows a summary of the experimental results for the elastic modulus and the
maximum tensile strength. Both are presented as an average value, which was obtained
by adding all the tests carried out for the same specimen and dividing this value by the
number of tests carried out on it. A comparison was made between the samples with and
without the addition of bentonite, defining the increase/decrease in the elastic modulus
and the maximum tensile strength.

Table 5. Summary of the results of the tensile test.

Specimen Elastic Module [MPa] Increase [%] Tensile Strength [MPa] Increase [%]
P 4674 - 20.2 -
H10 6373 - 19.11 -
B5H10 7858 23.30 14.68 −23.18
H15 5474 - 22.96 -
B5H15 7938 45.01 17.05 −25.74
H20 6016 - 22.14 -
B5H20 8409 39.78 20.16 −8.94
H25 7188 - 27.83 -
B5H25 7789 8.36 21.71 −21.99
H30 7161 - 33.90 -
B5H30 5510 −23.06 29.26 −13.69
H35 8384 - 27.00 -
B5H35 8737 4.21 34.28 26.96
H40 7055 - 28.16 -
B5H40 9065 28.49 26.77 −4.94
H45 6409 - 29.02 -
B5H45 9058 41.33 23.29 −19.75

The elastic modulus of the samples fabricated with the polymer and fibers did not
present a defined progressive increase, but there was an increase in its value as the per-
centage of fibers in the sample increased, where the best result of 8384 MPa was obtained
for H35.
The presence of bentonite contributed rigidity to the composite, and this could be
observed in the comparison between the pairs with and without the addition of bentonite,
where increases were perceived for almost all the combinations, except for the B5H30
samples, which showed a decrease of 23.06% compared to their peer H30. This result may
also have been influenced by the size of the bentonite particles, where authors such as
Seghar and Azem [24] also found that a small particle size increased the rigidity of the
material, while a larger one would favor the formation of agglomerates in the matrix. On
the other hand, it was possible to define that the tensile strength only increased in the
B5H35 samples with an increase of 26.96 % compared to its peer H35. This reduction
in mechanical resistance may be due to the agglomeration of the nanometric bentonite
particles, which may have led to poor dispersion in the polymer matrix. A similar behavior
was presented by Bahari et al. [30] and Khandelwal et al. [31].

3.4. Flexural Strength

Figure 8 presents the flexural test results for all species. Figure 8a shows the flexural
strength for the samples with the addition of fiber only, whereas Figure 8b shows the
flexural strength for the samples with the addition of fibers and bentonite. On the other
hand, in Figure 8c,d the elastic module for the samples with the addition of fiber only and
the samples with the addition of fibers and bentonite are presented, respectively. For each
specie, no less than five tests were carried out.
Polymers 2023, 15, x FOR PEER REVIEW 11 of 14

Polymers 2023, 15, 1571 11 of 14

particles, which may have led to poor dispersion in the polymer matrix. A similar behav-
ior was presented by Bahari et al. [30] and Khandelwal et al. [31].
In the samples manufactured only with the addition of fibers, the flexural resistance
only improved in the H40 and H45 samples with 85.22 MPa and 76.06 MPa, respectively,
3.4. Flexural Strength
compared to the results obtained for the polymer sample P, which was 69.05 MPa, as can
Figure
be seen 8 presents
in Figure themaximum
8a. The flexural test results
value wasfor all species.
found for the Figure 8a shows
H40 sample. Thethe flexural
presence of
strength
bentonitefor the samples
improved with thestrength
the flexural additionin of fiber only,
samples B5H20whereas FigureB5H30
(68.92 MPa), 8b shows theMPa),
(83.51 flex-
ural strength
B5H35 (98.04 for the and
MPa), samples
B5H45 with the addition
(79.55 MPa) with ofincreases
fibers andofbentonite. On54.50,
49.44, 63.26, the other
and hand,
4.59%,
in Figure 8c,d the elastic module for the samples with the addition of fiber only
respectively, with respect to their pairs H20 (46.12 MPa), H30 (51.15 MPa), H35 (63.87 MPa), and the
samples with the addition of fibers and bentonite are presented, respectively.
and H45 (76.06 MPa) and the polymer sample P (68.05 MPa), as can be seen in Figure 8b. For each
specie,
Similarno less than
results werefive testsbywere
found carried out.et al. [32].
Rapacz-Kmita

(a) (b)

(c) (d)
Figure 8. Flexural test results: (a) flexural strength of samples with the addition of fibers only; (b)
Figure 8. Flexural test results: (a) flexural strength of samples with the addition of fibers only;
flexural strength of samples with the addition of fibers and bentonite; (c) elastic module of samples
(b) flexural strength of samples with the addition of fibers and bentonite; (c) elastic module of
with the addition of fibers only; (d) elastic module of samples with the addition of fibers and ben-
samples with the addition of fibers only; (d) elastic module of samples with the addition of fibers
tonite.
and bentonite.
In the samples manufactured only with the addition of fibers, the flexural resistance
The elastic modulus, on the other hand, improved in all of the samples with the
only improved in the H40 and H45 samples with 85.22 MPa and 76.06 MPa, respectively,
addition of bentonite compared to their pairs containing the fiber and polyester polymer.
compared to the results obtained for the polymer sample P, which was 69.05 MPa, as can
The best result was obtained in the B5H35 (8453 MPa) samples with an increase of 139.26%
be seen in Figure 8a. The maximum value was found for the H40 sample. The presence of
compared to its pair B5H35 (35.33 MPa). The presence of 5 wt% of bentonite improved
bentonite improved the flexural strength in samples B5H20 (68.92 MPa), B5H30 (83,51
both the resistance and the elastic modulus when compared with the specimens that
MPa), B5H35
contained (98.04 and
polymer MPa), and B5H45
fibers, (79.55 MPa)
which agrees withresults
with the increases of 49.44,
obtained 63.26,where
by [28], 54.50,these
and
4.59%, respectively, with respect to their pairs H20 (46.12 MPa), H30 (51.15
improvements were perceived in a compound based on polymer and bentonite. A summary MPa), H35
(63.87
of the MPa),
resultsand
withH45
the(76.06 MPa)
average andof
values the polymer
the sample Pand
elastic modulus (68.05
theMPa), as strength
flexural can be seen
are
in Figure 8b. Similar
presented in Table 6. results were found by Rapacz-Kmita et al. [32]
The elastic modulus, on the other hand, improved in all of the samples with the ad-
dition of bentonite compared to their pairs containing the fiber and polyester polymer.
The best result was obtained in the B5H35 (8453 MPa) samples with an increase of 139.26%
Polymers 2023, 15, 1571 12 of 14

Table 6. Summary of the results of the flexural test.

Specimen Elastic Module [MPa] Increase [%] Flexural Strength [MPa] Increase [%]
P 3002 - 68.05 -
H20 4047 - 46.12 -
B5H20 6066 49.89 68.92 49.44
H25 3411 - 52.93 -
B5H25 6712 96.78 52.12 −1.53
H30 4427 - 51.15 -
B5H30 7268 64.17 83.51 63.26
H35 3533 - 63.87 -
B5H35 8453 139.26 98.04 53.50
H40 4073 - 85.22 -
B5H40 8296 103.68 69.23 −18.76
H45 4897 - 76.06 -
B5H45 8255 68.57 79.55 4.59

4. Conclusions
A novel composite material with a polyester polymer matrix reinforced with hemp
fibers and bentonite particles was manufactured, where the influence of the latter on the
mechanical properties such as tensile and flexural strength was determined. The percentage
of bentonite was set at 5%, while that of the hemp fibers ranged from 0% to 45%, and the
following conclusions can be drawn:
1. Bentonite clay improved the rigidity of the material, reporting an increase in the
elastic modulus, whose maximum value of 7938 MPa was found in the sample that
had an addition of 15% of fibers, which represents an increase of 45.01% with that
compared to its pair, which was made up of polyester polymer and fibers.
2. The tensile strength was affected by the addition of bentonite and all of the samples
showed a decrease compared to their peers. Except for the B5H35 sample, which
presented a value of 34.38 MPa, an increase of 26.96% with respect to its pair made of
polyester polymer and fibers.
3. The flexural elastic modulus improved in all of the samples with the addition of
bentonite when compared with similar ones that had reinforcing fibers. The best
result of 8453 MPa with an increase of 139.26% was found for a combination of the
35% addition of hemp fibers (B5H35 sample).
4. Flexural strength showed improvements when bentonite was added, except for cases
where it was combined with the 25 and 40% addition of hemp fibers. The maximum
value found of 83.51 MPa, which represents an increase of 63.26% with respect to its
pair composed of polyester polymer and hemp fibers, was found for a 30% addition
of fibers.
5. For all materials manufactured, either with the addition of fibers alone or with the
addition of fibers and bentonites, a good distribution of the fibers in the matrix was
achieved, and a good adhesion between the matrix and the fibers as well as the
absence of defects.

Author Contributions: Writing—original draft preparation, M.V.F.; Writing—review and editing,

M.V.F.; Methodology, M.J.A.G.; Conceptualization, R.B.O.; resources, J.L.V.R.; Supervision, A.R.S.;
Software, A.G.O.; Validation, C.G.K.; Formal analysis, A.A.A.; Supervision, F.R.V.D.; Visualization,
G.G.d.P. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Polymers 2023, 15, 1571 13 of 14

Conflicts of Interest: The authors declare no conflict of interest.

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