polymers

Article
Development of Hybrid Composite Utilizing Micro-Cellulose
Fibers Extracted from Date Palm Rachis in the Najran Region
Hassan Alshahrani 1, * , Basheer A. Alshammari 2 , Ahmer Hussain Shah 3 and Abdul Qadeer Dayo 3, *

1 Department of Mechanical Engineering, College of Engineering, Najran University, Najran 11001, Saudi Arabia
2 Materials Science Research Institute, King Abdulaziz City for Science and Technology, Riyadh 11442, Saudi Arabia
3 Faculty of Engineering and Architecture, Balochistan University of Information Technology, Engineering and
Management Sciences, Quetta 83700, Pakistan
* Correspondence: [email protected] (H.A.); [email protected] (A.Q.D.)

Abstract: Environmental effects can be reduced by using renewable resources in various applications.
The date palm fibers (DPF) used in this study were extracted from waste date ranches of the Najran
region by retting and manual peeling processes. The biocomposites were developed by reinforcing
the silane-treated DPF (SDPF) at different wt.% in eugenol phthalonitrile (EPN) and difunctional
benzoxazine (BA-a) copolymer. The impact strength, tensile, flexural, and dynamic mechanical
properties and thermogravimetric analysis were evaluated to understand the mechanical, thermome-
chanical, and thermal properties. Results confirmed that 30 wt.% SDPF-reinforced poly (EPN/BA-a)
composites produced the highest mechanical and thermomechanical properties, and were considered
optimized SDPF reinforcement. Furthermore, hybrid composites with 30 wt.% SDPF and 15 wt.%
silane-treated glass fibers (SGF) reinforcement having different lamination sequences were also stud-
Citation: Alshahrani, H.; ied. The lamination sequences showed a significant impact on the mechanical and thermomechanical
Alshammari, B.A.; Shah, A.H.; Dayo, properties, as properties were further enhanced by adding a core layer of SGF in hybrid composites.
A.Q. Development of Hybrid However, the thermal properties of SDPF/SGF laminates were higher than SDPF biocomposites,
Composite Utilizing Micro-Cellulose
but the SGF lamination sequence did not produce any impact. According to the limiting oxygen and
Fibers Extracted from Date Palm
heat resistance indexes, the developed SDPF/SGF laminates are self-extinguishing materials and can
Rachis in the Najran Region. Polymers
be used in temperature-tolerant applications up to 230 ◦ C.
2022, 14, 4687. https://doi.org/
10.3390/polym14214687
Keywords: date palm fibers; hybrid composites; mechanical properties; thermomechanical properties;
Academic Editors: Jose Gonzalo thermal properties
Carrillo Baeza, Pedro Jesús Herrera
Franco, Pedro Cortés, Eral Bele and
Eliana M. Agaliotis

Received: 9 October 2022 1. Introduction

Accepted: 1 November 2022 Evergreen date palm trees (Phoenix dactylifera L.) are widespread in the Middle East
Published: 3 November 2022 and the Arabian Peninsula due to the suitable climate. The date palm can easily survive an
Publisher’s Note: MDPI stays neutral
arid environment and provide enormous resources for nomadic tribes and local populations.
with regard to jurisdictional claims in The date palm tree requires special care and has a 40–50 year average life [1]. Worldwide,
published maps and institutional affil- there are approximately 105 million palm trees covering an area of 800,000 ha (FAO 2020).
iations. Based on the National Center Report for palm and dates, the total number of date palm
trees in the Najran region is around 385,623 trees. Every year, approximately 40 kg of
biomass from a single date palm tree is generated from offshoot, dead, or defective fronds.
The generated waste is burned or landfilled, which causes environmental pollution [2].
Copyright: © 2022 by the authors. Date palm waste is an excellent biomass source, as they have a low moisture content.
Licensee MDPI, Basel, Switzerland. Each year, Saudi Arabia generates over 345,000 tons of date palm waste: dry leaves, stems,
This article is an open access article pits/seeds, etc. [3]. During the past few decades, the demand for date fruit has increased
distributed under the terms and due to the cultural and traditional implications and increasing populations in the region
conditions of the Creative Commons
and other Islamic countries. Thus, the cultivation of this ancient crop in the Middle East
Attribution (CC BY) license (https://
has been dramatically increased and is expected to continue. As a result, the generation of
creativecommons.org/licenses/by/
date palm waste is expected to increase in the future [4].
4.0/).

Polymers 2022, 14, 4687. https://doi.org/10.3390/polym14214687 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 4687 2 of 19

The physiochemical, thermal, and biochemical techniques have been applied for the
sustainable utilization of date palm waste. The date palm waste is fibrous and primarily
composed of cellulose that has been lignin-embedded. Moreover, the date palm fibers
(DPF) have hollow channels due to the presence of lumen. The chemical composition
of biomass fibers shows the effects on various characteristics such as weather resistance,
degradation, fungi attack, etc. [5]. The date leaves, rachis, and stems are constituents of
cellulose (55–75%), lignin (≈15–30%), ash (≈2–10%), and extractive (≈5–8%) [5].
The enforcement of inflexible environmental legislation for the composite industry
has changed the momentum in favor of finding out environment-friendly reinforcements
and resin systems by maintaining performance similar to their synthetic counterparts.
Extensive research is being carried out on possible replacements for industrial fibers. In this
context, the use of DPF extracted from biomass waste has many advantages compared
to industrial fibers, such as carbon or glass fibers (GF). The advantages include ease and
economical availability, as they are renewable resources and consume a lower amount of
energy during the manufacturing process [6]. The use of extracted micro or nano DPF
will have positive environmental and economical effects. Various studies exist in the
literature on DPF reinforced composite, with low-density polyethylene [5,7], starch [8,9],
polypropylene [10,11], polyester [12], phenolic [13], and epoxy [14,15]. However, the effects
of DPF reinforcement in high performance thermosets are not studied.
Hybrid composites have more than single fiber materials in the same resin matrix.
Hybrid composites offer distinguishing properties that may or may not be present in
original elements. From the studies, it has been confirmed that the interplay hybridization
with synthetic fibers is a promising solution to overcome drawbacks that reduce the outdoor
applications of natural fiber-reinforced composite materials [16]. Several studies have been
reported on the mechanical and thermomechanical properties of hybrid composites made
with bio-based and synthetic fibers. Wang and coworkers evaluated the flax/GF sandwich
structured hybrid composites made with epoxy resin [17]. They stipulated that the flax
fibers as core and GF at the outer surface formation have the best thermomechanical and
mechanical properties. Kumar et al. [18] prepared brake pads with alkali-treated DPF
and compared the properties with traditional Kevlar-based brake pads. It was concluded
that the hybrid brake pads developed with 5 wt.% alkali-treated DPF and 45 wt.% Kevlar
fiber produced the best friction results. One most promising composite structure is a
sandwich structure that can enable fibers to maintain their level and trap air in micro
pockets, thus providing superior insulating properties along with lower weight and higher
strength. Alarifi studied the effects of the DPF collected from leaves, branches, and core-
shell on the prepared composites [19]. The epoxy date palm leaf composites had the best
mechanical performance among the examined composites.
Phthalonitrile (PN) resins synthesized from petroleum-based phenolate salts and
4-nitrophthalonitrile have exceptional physical properties. However, high melting points
(200–250 ◦ C), small processing windows, and fluctuating prices due to crude oil-based
raw materials are major concerns for the operational cost [20]. An easy and promising
alternative to crude oil-based monomers is to synthesize bio-based monomers by maintain-
ing their performance. Several bio-based PN monomers like guaiacol [21], cardanol [22],
eugenol (EPN) [21], and hydroxymethylated eugenol-based [23] PN monomers with cost-
effective fiber reinforced polymer composites fabrication process properties are reported
in the literature [21,22]. However, the high curing temperature and long curing time are
major drawbacks of these monomers. An easy and economical way to overcome the men-
tioned shortcoming is blending/copolymerization with new high-performance thermosets,
for instance, novolac [24], epoxies [25], and benzoxazine [26]. Recently, the EPN and difunc-
tional benzoxazine monomer (Bisphenol A-amine; BA-a) were copolymerized, and results
established that the complete curing can be achieved at 240 ◦ C in comparison to the pris-
tine poly (EPN) which needs to be cured at 350 ◦ C [21]. Moreover, the poly(BA-a/EPN)
copolymer had higher glass transition temperature (Tg ), stiffness, and thermal stabilities in
contrast to the virgin poly(BA-a) matrix [27].
Polymers 2022, 14, x FOR PEER REVIEW 3 of 20

Polymers 2022, 14, 4687 3 of 19

the poly(BA-a/EPN) copolymer had higher glass transition temperature (Tg), stiffness, and
thermal stabilities in contrast to the virgin poly(BA-a) matrix [27].
The current study focuses on the amalgamation using the BA-a/EPN copolymer as a
The current study focuses on the amalgamation using the BA-a/EPN copolymer as a
matrix to develop a composite laminate with silane-treated DPF obtained from biomass
matrix to develop a composite laminate with silane-treated DPF obtained from biomass
waste and hybrid composites with silane-treated glass fiber mat (SGF) by the compression
waste and hybrid composites with silane-treated glass fiber mat (SGF) by the compression
molding process. The prepared hybrid laminates are intended to be applied in exigent
molding process. The prepared hybrid laminates are intended to be applied in exigent
applications for instance used as structural parts in the marine industry. The mechanical,
applications for instance used as structural parts in the marine industry. The mechani-
thermomechanical, and thermal properties of biobased SDPF and SDPF/SGF hybrid com-
cal, thermomechanical, and thermal properties of biobased SDPF and SDPF/SGF hybrid
posites were vigilantly scrutinized.
composites were vigilantly scrutinized.
2.
2. Materials
Materials and
and Methods
Methods
2.1. Materials
Materials
For the current study, Jiangxi Huacui Advanced Materials Co., Ltd. (Jiujiang,
(Jiujiang, China)
China)
supplied the BA-a monomer. Aladdin Reagents Co. Ltd. (Shanghai, China)
supplied the BA-a monomer. Aladdin Reagents Co. Ltd. (Shanghai, China) delivered delivered eu-
genol (>99.0%),
eugenol (>99.0%),4-nitrophthalonitrile
4-nitrophthalonitrile(99.5%),
(99.5%),and
and3-glycidyloxypropyltrimethoxy
3-glycidyloxypropyltrimethoxy silane
agent (GPTM). GF mats with a plain-woven
plain-woven pattern,
pattern,200
200gsm,
gsm,and
and2.45 g/cm33 density
2.45g/cm density were
were
procured from Beijing Chuanjing
Chuanjing Co.,
Co., Ltd.
Ltd. (Beijing, China). All AR-grade solvents and
reagents used were supplied by Aladdin Reagents Co., Ltd. (Shanghai, China).

2.2. EPN
2.2. EPN Monomer
Monomer
The EPN
The EPN monomer
monomer synthesis
synthesis was
was carried
carried out
out in
in the
the potassium
potassium carbonate
carbonate presence
presence by
by
reacting eugenol
reacting eugenol and
and 4-nitrophthlonitrile,
4-nitrophthlonitrile, according
according to
to the
the reaction
reaction shown
shown in
in Scheme
Scheme 1,
1,
as suggested in prior work [21].
as suggested in prior work [21].

Scheme 1. Synthesis route for EPN monomer.

2.3. Fiber Isolation

2.3. Fiber Isolation
The waste date palm ranches (leaf stem) were collected from a local farm in Najran,
The waste date palm ranches (leaf stem) were collected from a local farm in Najran,
Saudi Arabia. The plant has an average of 15–25 ranches of 4–6 feet in length. The ranches
Saudi Arabia. The plant has an average of 15–25 ranches of 4–6 feet in length. The ranches
were shredded to 6–10 inch in length before any physical processing or chemical treatment.
were shredded to 6–10 inch in length before any physical processing or chemical treat-
The sand, dust, and other deposits attached to the ranches’ surface were removed by
ment. The sand, dust, and other deposits attached to the ranches’ surface were removed
washing several times with tap water, and were then immersed in warm water (50 ◦ C)
by washing several times with tap water, and were then immersed in warm water (50 °C)
for 24 h. Retting and manual peeling processes were employed to extract the DPF [28].
for 24 h. Retting and manual peeling processes were employed to extract the DPF [28].
The extracted DPF was ground in an ultra-fine grinder to achieve the micron size. The DPF
The
passedextracted
from 150 DPFµmwas ground
aperture in (100
size an ultra-fine grinder
mesh screen) to overnight
were achieve thesoaked
micronatsize. The
ambient
DPF passed from 150 µm aperture size (100 mesh screen) were overnight soaked
conditions in the acetone solution for the removal of containments from the surface and at ambi-
ent conditions
rinsed in the water.
with distilled acetoneLater,
solution for the
the DPF removal
were filteredofand
containments from thedried
overnight vacuum surface
at
and
110 C. Subsequently, the obtained DPF micro-fibers were stored in air-tight bagsdried
◦rinsed with distilled water. Later, the DPF were filtered and overnight vacuum and
at 110 °C. to
subjected Subsequently, the obtained DPF micro-fibers were stored in air-tight bags and
silane treatments.
subjected to silane treatments.
2.4. Silane Treatment of DPF and GF
2.4. Silane Treatment
The DPF surfaceofcontains
DPF andlignin,
GF pectin, and waxy substances, which must be removed
The DPF
to obtain surface
cellulose. contains
The lignin, pectin,
alkali treatment and waxyan
is considered substances,
economical which mustway
and easy be re-
to
moved
achievetolignin,
obtainpectin,
cellulose.
andThe alkali
waxy treatment is considered
substance-free an economical
fibers. However, andtreatment
the silane easy way
to achieve
method lignin,
gives pectin,
better and
results as waxy substance-free
compared fibers. However,
to alkali treatment [29]. the silane treatment
methodThegives
GPTM better results
silane as compared
coupling to alkali
agent solution treatment
was prepared[29].
by an amalgamation of 8 g
GPTM in 100 mL ethanol and 100 mL deionized water. The DPF were magnetically
stirred in the solution at ambient conditions for 6 h. Later on, DPF were filtered and the
coupling agents’ adverse impact was reduced by rinsing with ethanol and deionized water
Polymers 2022, 14, x FOR PEER REVIEW 4 of 20

The GPTM silane coupling agent solution was prepared by an amalgamation of 8 g

Polymers 2022, 14, 4687 GPTM in 100 mL ethanol and 100 mL deionized water. The DPF were magnetically stirred 4 of 19
in the solution at ambient conditions for 6 h. Later on, DPF were filtered and the coupling
agents’ adverse impact was reduced by rinsing with ethanol and deionized water solution
in solution
1:1. The silane-treated DPF (SDPF)DPF
in 1:1. The silane-treated were(SDPF)
vacuum dried
were at 85 °C
vacuum for 6ath85
dried ◦ Cstocked
and for 6 h in
and
anstocked
air-tightinbag. The same
an air-tight procedure
bag. was
The same followedwas
procedure to obtain
followedthetosilane-treated GF (SGF)
obtain the silane-treated
mat.
GFScheme 2 represents
(SGF) mat. Scheme the procedurethe
2 represents followed for the
procedure fiber extraction
followed for the fiberandextraction
composites and
preparation.
composites preparation.

Scheme
Scheme 2. Procedure
2. Procedure followed
followed forfor SDPF
SDPF fiber
fiber extraction
extraction and
and composites
composites preparation.
preparation.

2.5. Processing of SDPF Composites and SDPF/SGF Hybrid Composites

2.5. Processing of SDPF Composites and SDPF/SGF Hybrid Composites
The isothermal compression molding method was employed in the SDPF/copolymer
The isothermal compression molding method was employed in the SDPF/copolymer
and SDPF/SGF hybrid composites. The copolymer matrix was prepared by blending BA-a
and SDPF/SGF hybrid composites. The copolymer matrix was prepared by blending BA-
and EPN monomers in 6:4 for all samples. Different wt.% SDPF reinforced composites were
a and EPN monomers in 6:4 for all samples. Different wt.% SDPF reinforced composites
obtained by following the composition mentioned in Table 1.
were obtained by following the composition mentioned in Table 1.
The monomers were melted and homogenized on a hot plate, and the SDPF weight
Table 1. Formulation and stacking sequence of biobased composites and hybrid laminates.
amount as per the given composition mentioned in Table 1 was well mixed in the mono-
mer blend. Later on, the steel molds
BA-a EPNwith test sample dimensions were filled with
SDPF the
Stacking
Specimen Code SGF Vf
mixture. The mixture was[wt.%]
degassed[wt.%] [wt.%]
in a vacuum Sequence
oven at 140 °C for 4 h for voids revoking
from the cured composite.
Copolymer 60 The test 40
specimens were- cured at -160, 180, 200,
0 and 220 °C for
Uniform
2 h at each temperature 51
SDPF-15 on 12 MPa 34in an isothermal
15 compression
- molding
0.185 machine. The
Uniform
SDPF/SGFSDPF-30 42
hybrid composites with28copolymer 30 -
resins were also 0.355 following
prepared Uniform
the
SDPF-45 33 22 45 - 0.512
earlier mentioned procedure, only SGF mats were soaked in the monomer blends,Uniform
and the
2 Layer
stacking sequence of the33
H(SDPF/SGF)-1
sandwich hybrid
22
composites
30
is shown in Table
(7.5 wt.%
1. The following
0.458 ×
equation was used to determine the total fiber volume fraction (Vf) [30].
each layer)
(𝑤 ⁄𝜌(15)30 3 Layer
+ (𝑤 ⁄𝜌(5 )wt.%
H(SDPF/SGF)-2 𝑉
33 = 22 wt.% 0.458 ××
(1)
(𝑤 ⁄𝜌 ) + each ⁄𝜌 ) +each
(𝑤 layer) ⁄𝜌 )
(𝑤 layer)
Note: × = SDPF,  = SGF.
where w presents the weight in fraction and ρ presets the density. The subscripts D, G,
and M The
represent the respective
monomers values
were melted andofhomogenized
the SDPF, SGF,
onand copolymer
a hot plate, andmatrix.
the SDPF weight
amount as per the given composition mentioned in Table 1 was well mixed in the monomer
blend. Later on, the steel molds with test sample dimensions were filled with the mixture.
The mixture was degassed in a vacuum oven at 140 ◦ C for 4 h for voids revoking from the
cured composite. The test specimens were cured at 160, 180, 200, and 220 ◦ C for 2 h at each
Polymers 2022, 14, 4687 5 of 19

temperature on 12 MPa in an isothermal compression molding machine. The SDPF/SGF

hybrid composites with copolymer resins were also prepared following the earlier men-
tioned procedure, only SGF mats were soaked in the monomer blends, and the stacking
sequence of the sandwich hybrid composites is shown in Table 1. The following equation
was used to determine the total fiber volume fraction (Vf ) [30].

(w D /ρ D ) + (wG /ρG )
Vf = (1)
(w D /ρ D ) + (wG /ρG ) + (w M /ρ M )

where w presents the weight in fraction and ρ presets the density. The subscripts D, G,
and M represent the respective values of the SDPF, SGF, and copolymer matrix.

2.6. Characterization
2.6.1. FTIR
A Perkin Elmer Spectrum 100 spectrometer (Waltham, MA, USA) was used for the
confirmation of the silane treatment on the fibers’ surface; a thin sample film with KBr was
cast and evaluated in 4000–500 cm−1 region to obtain the Fourier transform infrared (FTIR)
spectrum of fibers.

2.6.2. Mechanical Properties

For the analysis of the mechanical properties of the developed composites, tensile,
flexural, and impact strength properties were evaluated. An impact resistance (IT503 Tinius-
Olsen, Shanghai, China) was used to estimate the impact strength, while the ASTM D256-
2010 standard was followed during testing. The Instron 5569 instrument (Norwood, MA,
USA) was used to evaluate the tensile and flexural (three-point bending) properties at 1 and
2 mm/min−1 crosshead speed, respectively, of 50 × 10 × 2 mm3 rectangular samples. For
a single code specimen, at least four replicas were tested and the average value is reported.

2.6.3. Dynamic Mechanical Analysis

The thermomechanical properties of developed biobased composites, hybrid laminates,
and pristine copolymer matrix samples with a dimension of 30 × 5 × 2 mm3 were evaluated
on a dynamic mechanical analyzer (DMA), Q800, TA Instruments (New Castle, DE, USA),
from 30 to 325 ◦ C at a 5 ◦ C/min heating ramp and 1 Hz frequency.

2.6.4. Thermal Stabilities

A TA Instruments Q50 (New Castle, DE, USA), was employed to determine the
thermal stabilities from 50 to 750 ◦ C in N2 purging (50 mL/min) of the developed biobased
composites, hybrid laminates, and pristine matrix samples at 20 ◦ C/min heating rate.

2.6.5. Water Absorption

ASTM D570-98 standard was followed for the estimation of water absorption of the
copolymer matrix, SDPF composite, and SDPF/SGF hybrid composites. Five rectangular
specimens for a single code were studied and water absorption was calculated from the
following formula.
(Wt − Wo )
Wu = 100% (2)
Wo
Here Wu represents the water uptake in percentage; while Wt is the weight of the
sample at time t and Wo represent the weight of the sample before initiating the test.

3. Results and Discussion

3.1. Effects of Silane Treatment on Fibers
The silane coupling agent increases the interfacial bonding between the natural fiber
and the matrix by reducing the cellulose hydroxyl groups of natural fiber. The silane-
treated fibers form covalent bonding between the fibers and matrix, this also prevents
 3. Results and Discussion
3.1. Effects of Silane Treatment on Fibers
The silane coupling agent increases the interfacial bonding between the natural fiber
Polymers 2022, 14, 4687 and the matrix by reducing the cellulose hydroxyl groups of natural fiber. The silane- 6 of 19
treated fibers form covalent bonding between the fibers and matrix, this also prevents the
swelling of fibers on exposure to moisture [31]. The chemical structure and thermal sta-
bilities before
the and after
swelling the fibers’
of fibers surfacetomodification
on exposure moisture [31]. were
Theevaluated
chemicalby employing
structure andthe
thermal
FTIR and TGA, respectively.
stabilities before and after the fibers’ surface modification were evaluated by employing
From the produced
the FTIR and TGA, FTIR curves in Figure 1, it can be easily observed that the silane
respectively.
treatment has
From effectively
the produced modified
FTIRthe fiberin
curves composition. Thebe
Figure 1, it can lignin (C=O
easily in the aromatic
observed that the silane
ring, at 1228 cmhas
treatment −1), pectin and wax (1735 cm−1), and hemicellulose (C=O, at 1648 and 1729
effectively modified the fiber composition. The lignin (C=O in the aromatic
cm−1) ring,
were at
reduced
1228 cm −1 ),Moreover,
[32]. pectin and thewax
silane(1735 cm−1 ), increased
treatment the intensity
and hemicellulose of the
(C=O, cel- and
at 1648
lulose1729
-OHcm −1 ) werepeak
stretching at 3417 cm −1. This suggests that the silane coupling agent en-
reduced [32]. Moreover, the silane treatment increased the intensity of
hanced thethe -OH concentration,
cellulose -OH stretching and reduced
peak at 3417 the −1 . This
cmfibers’ hydrophilic nature;
suggests that the these
silane-OH
coupling
groups willenhanced
agent enhance the the -OH
exposure to the matrix
concentration, for the the
and reduced interaction. Furthermore,
fibers’ hydrophilic the these
nature;
-OH groups
silane-DPF chemical will enhance
reaction was the exposureby
confirmed tothe
thepolysiloxane
matrix for the interaction.
network Furthermore,
in the SDPF by
the silane-DPF
the formation of O-Si-Ochemical
bondsreaction
(1120 cm was confirmed by the polysiloxane network in the SDPF
−1) [33].

by the formation of O-Si-O bonds (1120 cm−1 ) [33].

FigureFigure
1. FTIR1.spectra of untreated
FTIR spectra and silane-treated
of untreated fibers.fibers.
and silane-treated

Considering
Considering the FTIRthe spectra
FTIR spectra
of GF,ofthe
GF, the untreated
untreated GF has GFvery
hasfewverypeaks
few peaks confirming
confirming
lowerlower
numbernumber of specific
of specific functional
functional groups.
groups. This suggests
This suggests that thethatGF
thewill
GFhavewill have
lowerlower
physical
physical and chemical
and chemical interactions
interactions withwith
thethe matrix
matrix [34].
[34]. However,the
However, theSGF
SGFsurface
surface pro-
produced
−1
ducedseveral
severalspecific
specificfunctional
functionalgroupsgroupsatat1242,
1242,841,
841,909,
909,2943,
2943,and
and2836
2836cm cm−1,,representing
represent- the
existence
ing the existence of Si-O-Si, Si-C,Si-C,
of Si-O-Si, epoxy, CH2 ,CH
epoxy, and2, CH
and3 ,CH
respectively. Since Since
3, respectively. the silane groups can
the silane
groups can easily react with the generated hydroxyl groups during the resin curing SDPF
easily react with the generated hydroxyl groups during the resin curing process, pro- and
SGF fibers will have a strong chemical bond with the matrix
cess, SDPF and SGF fibers will have a strong chemical bond with the matrix [35]. [35].
The BA-a/EPN
The BA-a/EPN copolymer copolymer
is curedisatcured at atemperature
a higher higher temperature
range as range
compared as compared
to tra- to
traditional
ditional thermosetsthermosets
like epoxy likeorepoxy or phenolic
phenolic resins. resins.
DuringDuring the curing
the curing process,process, the natural
the natural
fibers will be exposed to the higher temperature, thus understanding
fibers will be exposed to the higher temperature, thus understanding the fibers’ behavior the fibers’ behavior at
elevated temperatures (thermal stability) is an important parameter. The thermal stabilities
of silane-treated DPF and GF were studied and the produced TGA results are illustrated in
Figure 2. The extracted data from TGA spectra are summarized in Table 2.
Polymers 2022, 14, x FOR PEER REVIEW 7 of 20

at elevated temperatures (thermal stability) is an important parameter. The thermal sta-

Polymers 2022, 14, 4687 bilities of silane-treated DPF and GF were studied and the produced TGA results are7 of
il-19
lustrated in Figure 2. The extracted data from TGA spectra are summarized in Table 2.

Figure 2. TGA thermograms in N2 environment of untreated and silane-treated fibers.

Figure 2. TGA thermograms in N2 environment of untreated and silane-treated fibers.
Table 2. TGA summary of untreated and silane-treated DPF and GF.
Table 2. TGA summary of untreated and silane-treated DPF and GF.
Sample T 5 [◦ C] T 10 [◦ C] Yc at 750 ◦ C [%]
Sample T5 [°C] T10 [°C] Yc at 750 °C [%]
Untreated DPF 236 282 19.88
Untreated
SDPF DPF 236
261 282 315 19.88 22.47
SDPFGF
Untreated 261
337 315 - 22.47 92.91
SGF
Untreated GF 285
337 - 421 92.91 88.92
SGF 285 421 88.92
The 5 and 10 wt.% loss temperatures (T5 and T10 ) of the untreated DPF were observed
Theand
at 236 5 and 28210◦wt.% loss temperatures
C, respectively. Moreover, (T5 and
a very T10)diminutive
of the untreated
weight DPF were
loss 100 ◦ C
observed
nearby
atconfirmed
236 and 282 °C,the
that respectively.
moisture was Moreover, a very
sufficiently diminutive
removed and DPFweightwas loss nearbystored
properly 100 °Cin
confirmed that the moisture was sufficiently removed and DPF was
airtight bags. After the silane treatment, the T5 and T10 values were increased to 261 and properly stored in
◦
airtight bags. After the silane treatment, the T and T values
315 C, respectively. Furthermore, a rise was recorded in the residual mass amount at
5 10 were increased to 261 and
315 °C, respectively.
higher temperaturesFurthermore,
known as chara yield rise was
valuerecorded
(Yc at 750 in◦ C).
the The
residual mass amount
introduction at
of a higher
higher
alkyl temperatures
chain length and knownsilylaspart
charofyield
GPTMS valuenot (Yonly
c at 750 °C). Thethe
increased introduction of a higher
thermal stability of the
alkyl
fiberchain length
but also and silyl
improved thepart of GPTMS not
hydrophobicity ofonly
SDPF increased
[36]. the thermal stability of the
fiber but
The also
GFimproved
is composed the hydrophobicity
of highly thermally of SDPFstable[36].
compounds i.e., SiO2 , Al2 O3 , MgO,
CaO,TheandGFZnO [37,38], therefore
is composed of highly the thermally
GF has excellent
stable thermal
compounds stability
i.e.,inSiO
comparison to DPF.
2, Al2O3, MgO,
◦
CaO, and ZnO T[37,38],
For instance, 5 and Ytherefore
c for the as-received
the GF has GF were about
excellent thermal337stability
C and 92.9%, respectively.
in comparison to
DPF. T5 and
The For Yc values
instance, recorded
T5 and for as-received
Yc for the silane-treated GFGF werewere slightly
about 337 °Clower
andin92.9%,
comparison
respec-to
the corresponding ◦ C and 88.92%, respectively.
tively. The T5 and Ycvalues valuesofrecorded
as-received GF and recorded
for silane-treated GFas 285 slightly
were lower in compar-
Thistocan
ison thebe attributed to the
corresponding attached
values organic compounds
of as-received after the as
GF and recorded silane
285 treatment, as they
°C and 88.92%,
can be easilyThis
respectively. degraded
can beatattributed
lower temperature [39]. The
to the attached FTIR and
organic TGA results
compounds afterconfirmed
the silanethe
effective treatment of silane coupling agents on DPF and GF.
treatment, as they can be easily degraded at lower temperature [39]. The FTIR and TGA
results confirmed the effective treatment of silane coupling agents on DPF and GF.
3.2. Mechanical Properties
3.2.1. Impact Properties
Figure 3 presents the comparison of impact properties of neat copolymer resin and
SDPF-reinforced composites. The impact strength value for the neat copolymer matrix
was estimated to be about 8.55 ± 0.82 kJ/m2 . Initially, on lower SDPF wt.% reinforce-
 3.2. Mechanical Properties
3.2.1. Impact Properties
Figure 3 presents the comparison of impact properties of neat copolymer resin and
Polymers 2022, 14, 4687 8 of 19
SDPF-reinforced composites. The impact strength value for the neat copolymer matrix
was estimated to be about 8.55 ± 0.82 kJ/m2. Initially, on lower SDPF wt.% reinforcement
(15 wt.%), a moderate increase (21.5%) was observed in the impact strength value. On
ment
further (15 wt.%),
increase a moderate
in the SDPF wt.%, increase
a huge(21.5%)
rise ofwas
82.3%observed in the impact
in the impact strengthstrength value.
of SDPF
reinforced composites was observed. However, 45 wt.% SDPF reinforced composite of
On further increase in the SDPF wt.%, a huge rise of 82.3% in the impact strength
SDPF
showed reinforced
a slight composites
decline wasstrength
in the impact observed. However,
values 45 wt.%
(8% lower SDPF reinforced
as compared compos-
to the SDPF-
ite showed a slight decline in the impact strength values (8% lower
30 sample). This suggests a gradual rise in the impact strength and the SDPF wt.%. More- as compared to the
SDPF-30 sample). This suggests a gradual rise in the impact strength
over, the impact strength of the 40 wt.% SDPF reinforced composite (SDPF-40) sample and the SDPF wt.%.
Moreover, the impact strength of the 40 wt.% SDPF reinforced composite
was 105% higher than that of the neat matrix. The decline in the impact strength as in the (SDPF-40) sample
was 105%
SDPF-45 sample higher than
case can bethat of thetoneat
credited poormatrix. The decline
fiber-matrix adhesion indue
the to
impact
a lowerstrength
amountas in
the SDPF-45 sample case can be credited to poor fiber-matrix adhesion due to a lower
of matrix volume, this agglomerates the fibers and decreases the energy needed for fiber
amount of matrix volume, this agglomerates the fibers and decreases the energy needed
pull-out [40].
for fiber pull-out [40].

Figure 3. Comparison
Figure of impact
3. Comparison strengthstrength
of impact of SDPF-reinforced biocomposites
of SDPF-reinforced and SDPF/SGF
biocomposites hybrid
and SDPF/SGF
composites.
hybrid composites.

The The
effect of SGF
effect hybrid
of SGF composites
hybrid compositeswithwith
optimum
optimumSDPFSDPFfraction and and
fraction various SGFSGF
various
sequences on the
sequences on impact strength
the impact is also
strength presented
is also in Figure
presented 3. The
in Figure SGFSGF
3. The hybrid composites
hybrid composites
produced
produceda further rise of
a further 7.65
rise of kJ/m in the2 impact
7.652 kJ/m strengthstrength
in the impact value invalue
contrast
in to the opti-
contrast to the
mum 30 wt.% SDPF reinforced composites. Additionally, the impact strength
optimum 30 wt.% SDPF reinforced composites. Additionally, the impact strength values values are
greatly
are affected by the modification
greatly affected in layup sequences
by the modification while maintaining
in layup sequences the same blend-
while maintaining the same
ing blending
ratio, as ratio,
in theascase of the
in the caseH(SDPF/SGF)-1
of the H(SDPF/SGF)-1and H(SDPF/SGF-2) specimens.
and H(SDPF/SGF-2) The
specimens.
H(SDPF/SGF)-2 specimenspecimen
The H(SDPF/SGF)-2 has a risehas of a4.08
rise kJ/m kJ/m2 instrength
2 in impact
of 4.08 compared
impact strength to the to
compared
H(SDPF/SGF)-1specimen.
the H(SDPF/SGF)-1specimen. A thin GF mat layer
A thin GF matin layer
the center
in theofcenter
the hybrid
of the composites in-
hybrid composites
creases the impact
increases resistance
the impact compared
resistance to theto
compared only
thethick
only layers outside.
thick layers outside.

3.2.2. Tensile Properties

All tensile stress-strain curves showed catastrophic failure with linear behavior up to
a certain point. Obtained curves of the pristine copolymerized matrix, SDPF reinforced
biocomposites, and SDPF/SGF hybrid composites are plotted in Figure 4. For a better
understanding of the relationship between tensile properties, a summary of obtained values
from tensile stress-strain curves is plotted in Figure 5.
 3.2.2. Tensile Properties
All tensile stress-strain curves showed catastrophic failure with linear behavior up to
a certain point. Obtained curves of the pristine copolymerized matrix, SDPF reinforced
biocomposites, and SDPF/SGF hybrid composites are plotted in Figure 4. For a better un-
Polymers 2022, 14, 4687 derstanding of the relationship between tensile properties, a summary of obtained values
9 of 19
from tensile stress-strain curves is plotted in Figure 5.

Polymers 2022, 14, x FOR PEER REVIEW 10 of 20

Figure 4. Tensile stress-strain curves of SDPF and SDPF/SGF hybrid composites.

Figure 4. Tensile stress-strain curves of SDPF and SDPF/SGF hybrid composites.

The lowest tensile strength (46.08 ± 2.98 MPa) and Young’s modulus (3.05 ± 0.20 GPa)
were observed for the pristine copolymer matrix, whereas it also had a higher strain to
failure among SDPF-reinforced composites. The highest tensile strength and Young’s
modulus values among SDPF reinforced composites were recorded on 30 wt.% SDPF re-
inforcement, the respective values were recorded as 67.15 ± 2.78 MPa and 5.07 ± 0.14 GPa.
On further SDPF reinforcement (45 wt.%), the tensile strength and modulus values were
slightly reduced due to the agglomeration which reduced the interfacial bonding between
fiber and copolymer resin [41] and recorded as 65.17 ± 3.45 MPa and 4.65 ± 0.21 GPa, re-
spectively.

Figure 5. A summary of tensile

Figure stress-strain
5. A summary curves
of tensile of SDPFcurves
stress-strain and SDPF/SGF
of SDPF andhybrid composites.
SDPF/SGF hybrid composites.

The lowest tensileThe

strength (46.08 ± 2.98
DPF microfibers wereMPa)
used and Young’s modulus
as reinforcing which±have
materials, (3.05 0.20aGPa)
lower elonga-
were observed fortion
the at
pristine
break. copolymer
Thus, the 45matrix, whereas
wt.% SDPF it alsocomposites
reinforced had a higher strainnearly
showed to fail-
15.3% and
ure among SDPF-reinforced
29.3% lowercomposites.
elongation atThe highest
break tensile strength
as compared andmatrix
to pristine Young’sandmodulus
SDPF/SGF hybrid
values among SDPF reinforced
composites, composites
respectively, were recorded
because GFs mat hason 30 wt.%
higher SDPF reinforcement,
elongation as compared to micro
SDPF.
the respective values Furthermore,
were recordedthe SDPF/SGF
as 67.15 ± 2.78
hybrid and 5.07 ±
MPacomposites showed a rapid
0.14 GPa. Onrise in stress to the
further
SDPF reinforcementmaximum value,the
(45 wt.%), followed
tensilebystrength
fracture failure, with thevalues
and modulus failure strain
were 37.1% higher
slightly re- than the
duced due to the agglomeration which reduced the interfacial bonding between fiber and ductility
SDPF reinforced composites. Thus, SDPF/SGF hybrid composites increase the
along
copolymer resin [41] andwith a rise inastensile
recorded 65.17 strength and and
± 3.45 MPa Young’s
4.65modulus.
± 0.21 GPa,The respectively.
GF have much higher
strength values as compared to the DPF. The lamination methods have a positive effect
on the tensile strength and Young’s modulus of hybrid composites. The inner layer SGF
hybrid composite showed an additional rise of 25% and 13% in the tensile strength and
Young’s modulus values, respectively, as compared to the recorded values for a tradi-
tional hybrid composite having SGF on the outer layers. Furthermore, in our earlier study,
we evaluated chopped SGF composites with poly(BA-a/EPN) copolymer having the same
Polymers 2022, 14, 4687 10 of 19

The DPF microfibers were used as reinforcing materials, which have a lower elonga-
tion at break. Thus, the 45 wt.% SDPF reinforced composites showed nearly 15.3% and
29.3% lower elongation at break as compared to pristine matrix and SDPF/SGF hybrid
composites, respectively, because GFs mat has higher elongation as compared to micro
SDPF. Furthermore, the SDPF/SGF hybrid composites showed a rapid rise in stress to
the maximum value, followed by fracture failure, with the failure strain 37.1% higher
than the SDPF reinforced composites. Thus, SDPF/SGF hybrid composites increase the
ductility along with a rise in tensile strength and Young’s modulus. The GF have much
higher strength values as compared to the DPF. The lamination methods have a positive
effect on the tensile strength and Young’s modulus of hybrid composites. The inner layer
SGF hybrid composite showed an additional rise of 25% and 13% in the tensile strength
and Young’s modulus values, respectively, as compared to the recorded values for a tra-
ditional hybrid composite having SGF on the outer layers. Furthermore, in our earlier
study, we evaluated chopped SGF composites with poly(BA-a/EPN) copolymer having
the same composition [42]. The tensile strength and Young’s modulus of the SDPF/SGF
sandwich structure were nearly 40 MPa and 2.5 GPa higher than the 40 wt.% chopped SGF
reinforced composite.

3.2.3. Flexural Properties

Polymers 2022, 14, x FOR PEER REVIEW 11 of 20
The flexural stress-strain curves of the biobased SDPF and hybrid SDPF/SGF compos-
ites are presented in Figure 6. A summary of obtained values from bending stress-strain
curves and a comparison with other studies is presented in Table 3.

Figure 6. Three-point bending stress-strain curves of SDPF and SDPF/SGF hybrid composites.
Figure 6. Three-point bending stress-strain curves of SDPF and SDPF/SGF hybrid composites.
The pristine matrix showed the lowest flexural strength (53.42 ± 3.69 MPa) and flexural
The pristine
modulus (2.03 ± matrix
0.32 GPa)showed
due tothe
thelowest
brittleflexural strength
nature of (53.42
the matrix. The± 3.69
SDPF MPa) and flex-
reinforcement
ural modulus (2.03 ± 0.32 GPa) due to the brittle nature of the matrix. The
in the copolymer improved the flexural strength and modulus and a decline was recorded SDPF reinforce-
ment
in theinbending
the copolymer improved the flexural strength and modulus and a decline was
strain values.
recorded in the bending
The hybridization with strain
GFsvalues.
had a positive effect on the SDPF composites. The bending
strain at break of the GF mat was much better than the SDPF, and the same was repli-
Table
cated3.inComparison of flexural properties
flexural stress-strain of the
curves. The SDPF and hybrid
SDPF/SGF SDPF/SGF reinforcedshowed
composites hybrid compo-
higher
sites with literature.
bending strain at break as compared to the pristine matrix and biobased SDPF compos-
Flexural Properties
Sample Code Reference
Strength [MPa] Modulus [GPa] Strain [%]
Copolymer 53.42 ± 3.69 2.03 ± 0.32 2.65 ± 0.07
Curr

SDPF-15 73.03 ± 5.32 3.12 ± 0.25 2.48 ± 0.09

Polymers 2022, 14, 4687 11 of 19

ites. However, the stress-strain curve of the SDPF/SGF hybrid composite showed a swift
rise in strength and a sudden reduction after reaching the maximum value. Moreover,
the results confirmed that the hybrid laminates have better values in comparison to SDPF
composites. Furthermore, from the plots it can be observed that H(SDPF/SGF)-1 and
H(SDPF/SGF)-2 specimens have the same blending ratio, however, the variation in layup
sequences significantly affected the flexural strength and modulus. The addition of the
intermediate layer further added 34.84 MPa and 1.45 GPa in flexural strength and modulus
values, respectively.

Table 3. Comparison of flexural properties of the SDPF and SDPF/SGF reinforced hybrid composites
with literature.

Flexural Properties
Sample Code Reference
Strength [MPa] Modulus [GPa] Strain [%]
Copolymer 53.42 ± 3.69 2.03 ± 0.32 2.65 ± 0.07
SDPF-15 73.03 ± 5.32 3.12 ± 0.25 2.48 ± 0.09
SDPF-30 107.82 ± 4.37 4.58 ± 0.25 2.39 ± 0.05
Current Work
SDPF-45 89.81 ± 6.16 4.79 ± 0.54 2.08 ± 0.06
H(SDPF/SGF)-1 168.71 ± 4.36 8.17 ± 0.35 2.51 ± 0.03
H(SDPF/SGF)-2 203.55 ± 4.71 9.62 ± 0.32 2.69 ± 0.04
Chopped GF-40 wt.% a 148.64 ± 4.36 7.74 ± 0.216 1.38 ± 0.04 [42]
Kevlar fiber-20 wt. % b 149.78 ± 7.4 6.89 ± 5.3 - [43]
Flax/basalt fiber c 144.8 8.27 - [44]
DPF/kenaf fiber d 56.24 4.77 - [45]
Jute/basalt fiber d 178.6 ± 2.9 10.60 ± 0.33 - [16]
Flax/GF d 390.19 13.56 - [17]
Carbon cloth e 756 119 0.9 [23]
aReinforced in poly(BA-a/EPN) copolymer in 6:4; b poly(BA-a) benzoxazine; c Vinyl ester; d Epoxy; e hydrox-
ymethylated eugenol PN.

Furthermore, the flexural properties of the hybrid composites were significantly higher
than the various studied composites; i.e., 40 wt.% chopped GF reinforced in BA-a/EPN
copolymer [42], 20 wt.% Kevlar Fiber reinforced in poly(BA-a) [43], and flax/basalt fibre
laminates with epoxy resin [44]. However, the flexural strength and modulus were signifi-
cantly lower than the flax/GF hybrid epoxy composites [17]. This can be attributed to the
usage of the flax fiber mats in earlier investigations, whereas the laminates in the current
study were made using micro SDPF fibers. These findings imply that the investigated com-
posites exhibit excellent properties and are suitable for usage in the demanding application
in structural engineering.

3.3. Thermomechanical Properties

During the selection of polymer-based materials for high-temperature applications,
the thermomechanical properties are significantly considered. The DMA is considered an
effective way to determine the thermomechanical properties of polymer-based materials,
such as the ability to retain stored energy. Thermomechanical properties of polymer-
based composites, exclusively depend on the reinforced material’s nature and morphology,
and generated interface between reinforcement and matrix [46]. Figure 7 presents the
storage modulus curves versus temperature of SDPF composites and SDPF/GF hybrid
composite with poly(BA-a/EPN) copolymer as a matrix, and the extracted data from the
DMA spectra are summarized in Table 4.
From the spectra plotted in the figure, we can easily scrutinize the enhancement in the
storage modulus (E’) due to the SDPF reinforcement till 30 wt.%. This can be attributed to
the stiffness imposed by the fibers primarily by the strength of the intermolecular forces and
stronger adhesion to the polymer chains at the fiber/matrix interface. The SDPF-45 sample
having 45 wt.% SDPF reinforcement showed nearly 4% lower E’ value as compared to
SDPF-30 sample. This observation is in good agreement with the earlier observed me-
 Polymers 2022, 14, 4687 12 of 19

chanical properties. On a rise in the temperature, a sharp fall in E’ value was observed
nearby the Tg due to the diffusion motion of the main chain segments known as Brow-
nian movements [47]. Moreover, the decline in E’ is very high for the neat copolymer
Polymers 2022, 14, x FOR PEER REVIEW 13 of 20
matrix in comparison to biobased or hybrid composites, due to the escalation in the me-
chanical restraint and hydrodynamic effects. The highest E’ value was recorded for the
H(SDPF/SGF)-2 hybrid laminate.

The
Figure7.7.The
Figure storagemodulus
storage moduluscurves
curvesofofSDPF
SDPFbiocomposites
biocompositesand
andSDPF/SGF
SDPF/SGF hybridlaminates
hybrid laminateswith
with
poly(BA-a/EPN) copolymer as a matrix.
poly(BA-a/EPN) copolymer as a matrix.

Table 4. Summary
From the spectra plottedtanindelta,
of stiffness, and effectiveness
the figure, coefficient
we can easily (C) fromthe
scrutinize DMA spectra of SDPF
enhancement in
biocomposites and SDPF/SGF hybrid laminates.
the storage modulus (E’) due to the SDPF reinforcement till 30 wt.%. This can be attributed
to the stiffness imposed E’ by@the fibers primarily
50 ◦ C, tan delta
by the strength of the intermolecular
Effectiveness Coefficient C forces
Sampleadhesion to the polymer chains
and stronger ◦ at the fiber/matrix interface. The SDPF-45
[MPa] [ C] 175 ◦ C 200 ◦ C 225 ◦ C
sample having 45 wt.% SDPF reinforcement showed nearly 4% lower E’ value as com-
pared Copolymer
to SDPF-30 sample. This2139 observation 225.5
is in good agreement - - earlier observed
with the -
SDPF-15 2611 229.8 0.76 0.55 0.41
mechanical properties. On a rise in the temperature, a sharp fall in E’ value was observed
SDPF-30 3448 235.1 0.68 0.50 0.39
nearby SDPF-45
the Tg due to the diffusion
3331
motion 231.1
of the main chain 0.72
segments 0.52
known as Brownian
0.42
movements [47]. Moreover,5190
H(SDPF/SGF)-1 the decline in233.7
E’ is very high0.71 for the neat copolymer
0.51 matrix
0.43 in
comparison to biobased or5533
H(SDPF/SGF)-2 hybrid composites,
232.8 due to the escalation in
0.70 the mechanical
0.51 0.43 re-
straint and hydrodynamic effects. The highest E’ value was recorded for the
H(SDPF/SGF)-2 hybrid laminate.
The reinforcing effect can be evaluated by computing the effectiveness coefficient (C),
The reinforcing effect can be evaluated by computing the effectiveness coefficient (C),
defined as the ratio between the E’ values in glassy and rubbery regions of the composites
defined as the ratio between the E’ values in glassy and rubbery regions of the composites
in relation to the pristine matrix, and represented by the following equation [48].
in relation to the pristine matrix, and represented by the following equation [48].
 
(E ⁄𝐸 r0 )
𝐸g0 /E
𝐶= Composite (3)
C = ( 𝐸 ⁄𝐸  ) (3)
0
Eg /Er 0
The coefficient C was computed at three temperatures Resin in the rubbery region (175, 200,
and 225 The°C), while the
coefficient E’ value
C was in theatglassy
computed region was kept
three temperatures constant
in the rubberyatregion
50 °C (175,
mostly200,
known
and 225as ◦stiffness.
C), while the E’ value in the glassy region was kept constant at 50 ◦ C mostly
From
known asthe analysis of C values for the SDPF-reinforced biobased composites, it can be
stiffness.
concluded that the C value decreases as the SDPF content increases till the optimized load-
ing. The lower C value signifies better effectiveness and advocates the higher stress trans-
fer between fiber and matrix. On 45 wt.% reinforcement either for biobased SDPF compo-
sites or hybrid (SDPF/SGF) laminates. The C values do not change, due to the possible
 Polymers 2022, 14, 4687 13 of 19

From the analysis of C values for the SDPF-reinforced biobased composites, it can
be concluded that the C value decreases as the SDPF content increases till the optimized
loading. The lower C value signifies better effectiveness and advocates the higher stress
Polymers 2022, 14, x FOR PEER REVIEWtransfer between fiber and matrix. On 45 wt.% reinforcement either for biobased 14 of
SDPF20
composites or hybrid (SDPF/SGF) laminates. The C values do not change, due to the
possible agglomeration caused by the increased volume fraction. Similar behavior is already
reported for pineapple leaf/GF
The reinforcements, [49] and
either fibers ramie fiber/GF
or particles, hybrid polyester
show significant impactscomposites
on the damp- [50].
The reinforcements, either fibers or particles, show significant impacts on the
ing factor (tan delta) spectra of the obtained composites. From the tan delta peak height and damping
Tgfactor
values, thedelta)
(tan spectra
possible of the obtained
filler-matrix adhesioncomposites. From the
can be estimated. Thetan deltafiller-matrix
weak peak heightad- and
T g values, the possible filler-matrix adhesion can be estimated. The
hesion produces a higher value for tan delta peak height and a lower Tg value. Whileweak filler-matrix
adhesion
stronger produces aadhesion
filler-matrix higher value for tan
produces delta
vice versapeak height
results dueand
to a lower
the Tg value.
limited mobility While
of
the polymer chains [46]. Figure 8 presents the damping factor curves of SDPF compositesof
stronger filler-matrix adhesion produces vice versa results due to the limited mobility
theSDPF/GF
and polymer hybrid
chains [46]. Figure 8 presents the damping factor curves of SDPF composites
composites.
and SDPF/GF hybrid composites.

Figure
Figure 8. 8.
TheThe damping
damping factor
factor spectra
spectra ofof SDPF
SDPF biocomposites
biocomposites and
and SDPF/SGF
SDPF/SGF hybrid
hybrid laminates.
laminates.

From the tan delta curves, it can be observed that the curves’ peak height decreased
From the tan delta curves, it can be observed that the curves’ peak height decreased
and shifted towards a higher temperature as the SDPF fiber content was gradually raised
and shifted towards a higher temperature as the SDPF fiber content was gradually raised
from 0 to 30 wt.%. The 45 wt.% SDPF reinforced biocomposites showed a slightly higher
from 0 to 30 wt.%. The 45 wt.% SDPF reinforced biocomposites showed a slightly higher
damping factor peak. The lower peak height indicates good interfacial adhesion [51].
damping factor peak. The lower peak height indicates good interfacial adhesion [51].
Moreover, the curve width also becomes broader upon fiber addition. The H(SDPF/SGF)-2
Moreover, the curve width also becomes broader◦ upon fiber addition. The H(SDPF/SGF)-
hybrid laminates showed the highest Tg (233 C). The Tg value of hybrid laminates was
2 hybrid laminates showed the highest Tg (233 °C). The Tg value of hybrid laminates was
slightly lower than the SDPF-30 biobased composites. Similar observations were recorded
slightly lower than the SDPF-30 biobased composites. Similar observations were recorded
for empty fruit bunch/jute hybrid epoxy laminates [52], and pineapple/glass hybrid
for empty fruit
polyester bunch/jute
laminates hybrid epoxy
[49]. Researchers laminates
dedicated [52],
this and pineapple/glass
decline hybrid
in Tg due to lower poly-
fiber/matrix
ester laminates [49]. Researchers dedicated
interaction on the lower volume of the matrix.this decline in Tg due to lower fiber/matrix

interaction on the lower volume of the matrix.

3.4. Thermal Properties
3.4. Thermal Properties
Thermal stability behavior of the developed biobased SDPF and SDPF/SGF hybrid
Thermallaminates
composite stability behavior of the developed
were scrutinized through biobased
TGA in an SDPF and SDPF/SGFproduced
N2 environment; hybrid
composite laminates were scrutinized through TGA in an N environment; produced spec-5.
spectra are illustrated in Figure 9, and a summary of the TGA data is presented in Table
2

tra are illustrated in Figure 9, and a summary of the TGA data is presented in Table 5.

Table 5. TGA summary of SDPF biocomposites and SDPF/SGF hybrid laminates.

Sample T5 [°C] T10 [°C] Yc [%] HRI [°C] LOI [%]

 lose, lignin, and pectin were decomposed [53] and had lower thermal stability compared
to the matrix. These observations trend is in good agreement with the thermals stability
of DPF/epoxy composites recorded by Gheith and coworkers [54]. However, the
DPF/epoxy composites showed a 25 wt.% decline at around 300 °C. In the current study,
Polymers 2022, 14, 4687 the improved thermal stabilities as compared to DPF/epoxy composites can be dedicated
14 of 19
to the formed isoindoline and triazine structure during copolymer curing [55].

Figure
Figure 9. 9. Thermal
Thermal stability
stability spectra
spectra of SDPF
of SDPF biocomposites
biocomposites andand SDPF/SGF
SDPF/SGF hybrid
hybrid laminates
laminates in N2in
N2 atmosphere.
atmosphere.

Furthermore,
Table the SDPF/SGF
5. TGA summary hybrid composites
of SDPF biocomposites showed
and SDPF/SGF a riselaminates.
hybrid in T5, T10, Yc, HRI, and
LOI values in contrast to SDPF-30 and SDPF-45 specimens. These composites have 30 and
T 5 [◦ C] ◦ ◦ C]
45 wt.%Sample
SDPF reinforcement, while theT hybrid Yc [%]
10 [ C] composites have 30HRIand[ 15 LOI [%]
wt.% reinforce-
Copolymer 427.6 455.2 66.10 270.21
ment of SDPF and SGF, respectively. Synthetic fibers such as SGF have higher thermal 43.94
stability in comparison to lignocellulosic-based natural fibers [56]. Thus, the initial42.28
SDPF-15 398.0 431.5 61.96 221.48 degra-
SDPF-30 360.5 423.8 56.14 208.84 39.95
dation and residue values were significantly raised and recorded as 364.8 °C, 438.3 °C,
SDPF-45 341.6 416.5 50.60 204.25 37.74
and H(SDPF/SGF)-1
60.89 for T5, T10, and Y c values, respectively. The lamination sequence does not show
364.8 438.3 60.89 230.26 41.85
H(SDPF/SGF)-2 365.3 439.9 60.85 230.35 41.84

From the TGA spectra for pristine copolymer matrix, biobased and hybrid composites,
without any doubt, it can be observed that all composites and laminates have lower
thermal stabilities than the matrix. Moreover, the copolymer matrix showed higher values
for initial degradation (T5 and T10 ) and Yc . The recorded values were read as 427.6 ◦ C,
455.2 ◦ C, and 66.1%, respectively. These values were achieved due to the much better cross-
linking of PN and polybenzoxazine resin. The thermal stability of biobased composites
was gradually reduced as the SDPF reinforcement was raised from 0 to 45 wt.%, and a
decline of 86 ◦ C, 38.7 ◦ C, and 15.5% were recorded in T5 , T10 , and Yc values, respectively.
The SDPF are lignocellulosic fibers; on exposure to a higher temperature; the hemicellulose,
lignin, and pectin were decomposed [53] and had lower thermal stability compared to
the matrix. These observations trend is in good agreement with the thermals stability of
DPF/epoxy composites recorded by Gheith and coworkers [54]. However, the DPF/epoxy
composites showed a 25 wt.% decline at around 300 ◦ C. In the current study, the improved
thermal stabilities as compared to DPF/epoxy composites can be dedicated to the formed
isoindoline and triazine structure during copolymer curing [55].
Furthermore, the SDPF/SGF hybrid composites showed a rise in T5 , T10 , Yc , HRI,
and LOI values in contrast to SDPF-30 and SDPF-45 specimens. These composites have
30 and 45 wt.% SDPF reinforcement, while the hybrid composites have 30 and 15 wt.%
reinforcement of SDPF and SGF, respectively. Synthetic fibers such as SGF have higher
Polymers 2022, 14, 4687 15 of 19

thermal stability in comparison to lignocellulosic-based natural fibers [56]. Thus, the initial
degradation and residue values were significantly raised and recorded as 364.8 ◦ C, 438.3 ◦ C,
and 60.89 for T5 , T10 , and Yc values, respectively. The lamination sequence does not show
any impact on the thermal stability as both samples have the same composition. These can
be dedicated to the better dispersion of fibers and accuracy during sample curing.
Heat resistance and limiting oxygen indexes (HRI and LOI) are very important terms
to identify the limitation of the composites’ application. The HRI identifies the physical
heat (temperature) tolerance limitation, while the LOI value > 26 indicates the excellent self-
extinguishing and flame retardancy properties of the materials. The following relationships
were calculated for the estimation of HRI and LOI, respectively [57].

HRI = 0.49[ T5 + 0.6( T30 − T5 )] (4)

LOI = 17.5 + 0.4 Yc (5)

From the calculated values as summarized in Table 5, we can easily analyze that
the pristine copolymer matrix has a very high value for HRI and LOI, confirming the
high-temperature tolerance and excellent self-extinguishing properties of the copolymer.
Moreover, after the reinforcement of SDPF, the HRI and LOI values sharply decrease due to
the lower thermal stabilities of reinforced material. The lowest HRI and LOI value among
the studied biobased composites were observed for the SDPF-45 specimen having 45 wt.%
SDPF reinforcement and recorded values were read as 204.25 ◦ C and 37.74%, respectively.
This suggests that the biobased SDPF composite laminates can be used up to 200 ◦ C
and have excellent self-extinguishing properties. Furthermore, the hybrid SDPF/SGF
composite laminates showed a rise in the HRI and LOI value, and values were calculated
to be 230.26 ◦ C and 41.85%, respectively. This can be easily attributed to the synthetic
fiber reinforcement having higher thermal stabilities as compared to the SDPF fiber [58].
Moreover, the HRI value of the hybrid composite is nearly the same as reported for the
30 wt.% carbon fiber reinforced in (dicyanate ester/benzoxazine) copolymer by Zegaoui
and coworkers [59]. These observations are in favor of the TGA discussed earlier.

3.5. Water Absorption

One of the critical challenges for natural fiber-reinforced composites is moisture
susceptibility. The fiber-matrix interfacial interaction is weakened due to the absorbed water,
and it ultimately reduces the mechanical properties[60]. The weight gain in percentage
at room temperature as a function of the square root of time of SDPF biocomposites and
SDPF/SGF hybrid composites is produced in Figure 10.
As expected, a gradual rise in the moisture absorption for SDPF biocomposites and
SDPF/SGF hybrid composites continued till saturation was attained, however the moisture
transport rate was reduced as the time of immersion was increased. The lowest moisture
(1.26 ± 0.09%) was absorbed by the pristine matrix, whereas 45 wt.% SDPF reinforced
composites absorb the highest moisture by 6.57 ± 0.12%. However, the lowest value
(3.03 ± 0.11%) among the SDPF composites was recorded for the 15 wt.% SDPF, even after
the saturation time. The SDPF/SGF hybrid composites also showed lower values com-
pared to the SDPF-30 sample. Modest moisture absorption (4.02 ± 0.11%) was observed
for H(SDPF/SGF)-1 sample having SGF mat on the outer side. However, the hybrid
composites with an SGF mat on the outer side and core showed a slightly higher value
(3.30 ± 0.1%) than the SDPF-15 sample, even though the sample contains 30 wt.% of SDPF.
This confirms that moisture absorption can be reduced by an interlaminar layer of synthetic
fiber in biocomposites.
The natural fibers such as DPF have -OH and contain amorphous regions which
facilitate the water molecules’ diffusion and break the hydrogen bonds. Therefore, an in-
termolecular distance is created in the cellulose chains and consequently, the fibers are
swollen [61].On the other hand, synthetic fibers like SGF do not absorb moisture from the
surrounding environment or on water immersion [62]. Therefore, the affinity to absorb
Polymers 2022, 14, 4687 16 of 19

moisture by the hybrid laminates having SGF layers on the outer surface was sufficiently
reduced. Similar observations were recorded by Cheng et al. in the durability study of
carbon/flax fiber hybrid biocomposites with polypropylene matrix [40]. They concluded
that the synthetic fibers sufficiently decline the water absorption, and the carbon/flax
Polymers 2022, 14, x FOR PEER REVIEW 17 fibers
of 20
hybrid composites having interlaminar carbon fiber mat layer obtained the lowest water
absorption value (around 12.5%).

Figure 10. Water uptake behavior of SDPF and SDPF/SGF hybrid composites.
Figure 10. Water uptake behavior of SDPF and SDPF/SGF hybrid composites.
4. Conclusions
The
The natural fibers such
reinforcement as DPF
of SDPF have
fibers -OH andfrom
extracted contain
wasteamorphous
date palmregions
rancheswhich fa-
and the
cilitate the water molecules’ diffusion and break the hydrogen bonds.
production of SDPF/SGF hybrid laminates in high performance poly (EPN/BA-a) ther- Therefore, an inter-
molecular
mosets were distance is created
outlined in the in the cellulose
current work. Thechains and consequently,
biocomposites the fibers
produced are swol-
by 15–45 wt.%
SDPF
len [61] .On the other
reinforcement showed
hand, that the mechanical
synthetic fibers likeproperties
SGF do not were gradually
absorb enhanced
moisture from and
the
reduced afterenvironment
surrounding the optimizedorreinforcement of 30 wt.%
on water immersion SDPF.
[62]. However,
Therefore, thethe thermal
affinity to proper-
absorb
ties were by
moisture significantly
the hybridreduced
laminatesdue to theSGF
having incorporation
layers on theof the lowsurface
outer thermally-stable SDPF
was sufficiently
compared to the copolymer matrix, as evidenced by the TGA results.
reduced. Similar observations were recorded by Cheng et al. in the durability study of For enhancement of
the mechanical, thermomechanical, and thermal properties, SDPF/SGF
carbon/flax fiber hybrid biocomposites with polypropylene matrix [40]. They concluded hybrid laminate
withthe
that 30 and 15 wt.%
synthetic reinforcement
fibers sufficientlyofdecline
SDPF and the SGF,
waterrespectively,
absorption,andanddifferent lamination
the carbon/flax fi-
sequences
bers hybridwere also developed.
composites having The developedcarbon
interlaminar SDPF/SGFfiber hybrid laminates
mat layer obtainedshowed much
the lowest
better absorption
water mechanical,valuethermomechanical,
(around 12.5%). and thermal properties. The mechanical and thermo-
mechanical properties were significantly enhanced by adding a core layer of SGF in hybrid
laminate.
4. Moreover, the lamination sequence does not show any impact on the thermal
Conclusions
properties. From the HRI and LOI values, it was confirmed that the developed SDPF/SGF
The reinforcement of SDPF fibers extracted from waste date palm ranches and the
laminates have high-temperature tolerance (230 ◦ C) and self-extinguishing properties.
production of SDPF/SGF hybrid laminates in high performance poly (EPN/BA-a) thermo-
sets were outlined in the current work. The biocomposites produced by 15–45 wt.% SDPF
Author Contributions: Conceptualization, H.A. and A.Q.D.; methodology, H.A. and A.Q.D.; formal
reinforcement
analysis, A.Q.D.showed
and A.H.S.;thatinvestigation,
the mechanical H.A.,properties wereand
A.Q.D., B.A.A. gradually enhancedH.A.
A.H.S.; resources, and and
re-
duced after the optimized reinforcement of 30 wt.% SDPF. However, the thermal
A.Q.D.; writing—original draft preparation, H.A. and A.Q.D.; writing—review and editing, A.H.S. proper-
ties
and were significantly
B.A.A.; visualization,reduced
A.Q.D.due
and to the incorporation
A.H.S.; of the lowH.A.
project administration, thermally-stable SDPF
and A.Q.D.; funding
compared
acquisition,to theAll
H.A. copolymer matrix,
authors have read as
andevidenced by published
agreed to the the TGA results. For
version of theenhancement
manuscript. of
the mechanical, thermomechanical, and thermal properties, SDPF/SGF hybrid laminate
with 30 and 15 wt.% reinforcement of SDPF and SGF, respectively, and different lamina-
tion sequences were also developed. The developed SDPF/SGF hybrid laminates showed
much better mechanical, thermomechanical, and thermal properties. The mechanical and
thermomechanical properties were significantly enhanced by adding a core layer of SGF
in hybrid laminate. Moreover, the lamination sequence does not show any impact on the
thermal properties. From the HRI and LOI values, it was confirmed that the developed
Polymers 2022, 14, 4687 17 of 19

Funding: This research was funded through a project grant code (NU/NAR/SERC/11/3) under
the Najran Region Research Program Funding, deanship of scientific research at Najran University,
Saudi Arabia.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Acknowledgments: The authors are thankful to the Scientific Research at Najran University for
funding this work under the Najran Region Research Program Funding, program grant code
(NU/NAR/SERC/11/3).
Conflicts of Interest: The authors declare that they have no conflict of interest.

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