polymers

Article
Mechanical, Thermal, and Fire Retardant Properties of Rice
Husk Biochar Reinforced Recycled High-Density Polyethylene
Composite Material
Atta ur Rehman Shah 1 , Anas Imdad 2 , Atiya Sadiq 2 , Rizwan Ahmed Malik 3 , Hussein Alrobei 4, *
and Irfan Anjum Badruddin 5

1 Department of Mechanical Engineering, COMSATS University Islamabad, Wah Campus,

Wah Cantt 47040, Pakistan
2 Department of Mechanical Engineering, HITEC University, Taxila 47050, Pakistan
3 Department of Metallurgy & Materials Engineering, Faculty of Mechanical and Aeronautical Engineering,
University of Engineering and Technology, Taxila 47050, Pakistan
4 Department of Mechanical Engineering, College of Engineering, Prince Sattam bin Abdullaziz University,
AlKharj 11942, Saudi Arabia
5 Department of Mechanical Engineering, College of Engineering, King Khalid University,
Abha 61421, Saudi Arabia
* Correspondence: [email protected]

Abstract: This study concentrated on the influence of rice husk biochar on the structural, thermal,
flammable, and mechanical properties of recycled high-density polyethylene (HDPE). The percentage
of rice husk biochar with recycled HDPE was varied between 10% and 40%, and the optimum
percentages were found for the various properties. Mechanical characteristics were evaluated in
terms of the tensile, flexural, and impact properties. Similarly, the flame retardancy of the composites
was observed by means of horizontal and vertical burning tests (UL-94 tests), limited oxygen index,
and cone calorimetry. The thermal properties were characterized using thermogravimetric analysis
Citation: Shah, A.u.R.; Imdad, A.;
(TGA). For detailed characterization, Fourier transform infrared spectroscopy (FTIR) and scanning
Sadiq, A.; Malik, R.A.; Alrobei, H.;
electron microscopy (SEM) tests were performed, to elaborate on the variation in properties. The
Badruddin, I.A. Mechanical, Thermal,
composite with 30% rice husk biochar demonstrated the maximum increase in tensile and flexural
and Fire Retardant Properties of Rice
Husk Biochar Reinforced Recycled
strength, i.e., 24% and 19%, respectively, compared to the recycled HDPE, whereas the 40% composite
High-Density Polyethylene showed a 22.5% decrease in impact strength. Thermogravimetric analysis revealed that the 40% rice
Composite Material. Polymers 2023, husk biochar reinforced composite exhibited the best thermal stability, due to having the highest
15, 1827. https://doi.org/ amount of biochar. In addition, the 40% composite also displayed the lowest burning rate in the
10.3390/polym15081827 horizontal burning test and the lowest V-1 rating in the vertical burning test. The 40% composite
material also showed the highest limited oxygen index (LOI), whereas it had the lowest peak heat
Academic Editors: Rosane Michele
Duarte Soares and Vsevolod
release rate (PHRR) value (52.40% reduced) and total heat release rate (THR) value (52.88% reduced)
Aleksandrovich Zhuikov for cone calorimetry, when compared with the recycled HDPE. These tests proved that rice husk
biochar is a significant additive for enhancing the mechanical, thermal, and fire-retardant properties
Received: 18 February 2023
of recycled HDPE.
Revised: 30 March 2023
Accepted: 31 March 2023
Keywords: polymer composites; recycled high density polyethylene; rice husk biochar; mechanical
Published: 9 April 2023
properties; thermal properties

Copyright: © 2023 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
This article is an open access article Global demand for fossil fuels is constantly increasing, but a huge challenge that
distributed under the terms and the world has to resolve is their rapid depletion with the passage of time, along with
conditions of the Creative Commons the excessive pollution caused [1,2]. This is why people are shifting towards the use of
Attribution (CC BY) license (https://
renewable materials, particularly due to environmental concerns and the future scarcity
creativecommons.org/licenses/by/
of petroleum-based products [3]. On the other hand, the demand for food for the world’s
4.0/).

Polymers 2023, 15, 1827. https://doi.org/10.3390/polym15081827 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 1827 2 of 17

population is increasing day by day, which has caused the accumulation of agricultural
waste, and the most common way to get rid of this is to dispose of or incinerate it [4].
Disposing of this waste poses serious threats to environmental safety and hygiene. How-
ever, the biomass can be converted into products and energy [5]. Employing these various
agricultural wastes in different composite materials could help alleviate this problem and
represents a great solution for recycling and resource conservation [6]. Several types of
organic waste, such as waste paper sludge and wool, have already been used to produce
biocomposites [7–10]. However, researchers are now inclining towards the development
of biochar from agricultural waste and utilizing it in composite materials, to improve the
desirable mechanical, thermal, and fire-retardant properties. When any type of biomass
is heated with an absence/limited supply of oxygen (pyrolysis), it will leave behind a
porous carbonaceous material, with the volatile gases absent, thus resulting in biochar
formation [11]. Biochar is composed of highly ordered turbostatically crystalline regions,
accompanied by some random amorphous regions [12], owing to the presence of cellulose.
This isotropic structure results in spaces that form a porous structure, just like a honeycomb
structure [13]. The reviews carried out by Väisänen et al. and Mohanty et al. gave a fair
idea of how effective biochar can be in a composite material [14,15].
Ayrilmis et al. analyzed the mechanical properties of a wood–plastic composite
(Polypropylene with Maleic Anhydride-grafted Polypropylene and different mixtures of
wood flour and charcoal flour) [16]. An investigation was performed to find the optimum
biomass for biochar-based polypropylene composites with rice husk, course wool, coffee
husk, and landfilled wood as biomasses and biochar made from landfill wood [17]. The
wood-based composite exhibited the best mechanical properties, with rice husk coming
second. Zhang et al. examined the incorporation of rice husk biochar into high-density
polyethylene and then compared this with wood–plastic composites [18]. It was found
that the biochar-reinforced plastic composites had much superior mechanical properties
to the wood–plastic composites. Sundarakannan et al. reinforced sugarcane biochar with
polyester resin [19]. The study also focused on the development of a biocomposite by
reinforcing a cashew nut shell biochar with unsaturated polyester resin at different load-
ings [20]. Huber et al. investigated the effect of the particle size of miscanthus biochar
on Polyamide polymer and found that particle size varied the mechanical properties of
the composite to an appreciable extent [21]. Khan et al. studied the influence of biochar
addition to epoxy resin and compared this with the addition of carbon nanotubes in an
epoxy matrix [22]. The biochar-reinforced epoxy composites outperformed the carbon
nanotube-reinforced epoxy composites, in terms of the mechanical properties. Bartoli et al.
tested the mechanical characteristics of an epoxy-based composite with five different types
of commercial biochar (rice husk, mixed softwood, miscanthus, oil seed rape, and wheat
straw) [23]. Pandey et al. focused on the study of a biochar hybrid composite with sisal
fiber, softwood biochar, and epoxy as resin [24]. Similarly, Ketabchi et al. carried out
an analysis of varied amounts of biochar (made of oil palm empty fruit bunch fiber) in
polypropylene/ethylene-vinyl acetate, to form a hybrid composite [25]. They found that
30% biochar was preferable for enhancing the mechanical properties without degrading the
thermal properties. Zhang et al. evaluated the influence of rice husk biochar on the dynamic
mechanical properties of a composite [26]. The study revealed that biochar had a positive
effect on the creep resistance, dynamic viscoelasticity, and stress relaxation properties of
the composite. However, as the testing temperature increased, the stress relaxation and
creep resistance started to reduce. Bajwa et al. treated high-density polyethylene–wood
fiber composites with maleic anhydride polyethylene (MAPE) and found an improvement
in the mechanical properties of the biocomposite [27]. However, concern about the undesir-
able increase in the overall cost of production was also reported, owing to the expensive
compatibilizers used.
Das et al. reported that the addition of biochar to a composite could increase the thermal
stability and flame retardance to an excellent extent compared to the neat composite [1,2].
Time to ignition (TTI) and PHRR were significantly reduced with increased biochar contents,
Polymers 2023, 15, 1827 3 of 17

whereas the THR did not vary significantly. Das et al. also introduced wood and biochar
into polypropylene, with two flame retardants (FRs): magnesium hydroxide (Mg(OH)2 )
and ammonium polyphosphate (APP) [28]. They concluded that less wood and a higher
proportion of biochar was optimum for reducing flammability. Another research work by
Das et al. considered the addition of wood-waste-derived activated biochar to polypropy-
lene and revealed that the biochar was extremely effective in increasing the thermal stability
and reducing the flammability of the PP. Dahal et al. converted wood pellets into biochar
and then added this to epoxy. The study concluded that an increased biochar loading
had a better tendency to retard fire [29]. Li et al. studied the addition of nano charcoal
in polypropylene composites and found that an increase in the degradation temperature
led to an increase in the overall thermal properties of the composites [30]. Zhang et al.
also observed an enhancement in the thermal degradation temperature with rice husk
biochar filled composites [31]. Bartoli and Arrigo et al. performed TGA on polylactic acid
composites (PLA) [32]. They concluded that the addition of biochar increased the thermal
properties of the composites, but at higher filler loadings, they started to decrease, due
to agglomeration.
The quality of a biochar can adversely affect the mechanical properties of biocom-
posites. Das et al. stated that the most crucial factor in the performance of biochar-based
composites, and what makes them so promising, is the carbon content and the surface
area of the biochar [1,2]. Similar results were derived by Ho et al., in which they stated
that a high surface area of biochar, which results from high temperature pyrolysis, usually
assists in achieving the optimum dispersion of biochar particles in the polymer matrix [3].
Tomczyk et al. stated that increasing the pyrolysis temperature increased the carbon content
and specific surface area of biochar [33]. Das et al. studied the quality of biochars made in
different pyrolysis reactors [34]. They revealed that different types of pyrolysis reactors
yielded different qualities of biochar, and the utilization of these reactors to produce biochar
should be aligned with the intended application. However, among the operating condi-
tions, temperature is most important, as it primarily controls the properties and quality,
and adversely affects the yield of biochar produced during the process [35–38]. The effect
of pyrolysis temperature on the quality of biochar was studied by Elnour et al., in terms
of the morphological properties, physical properties, and biochar structure [39]. Zhang
et al. also conducted research regarding the addition of rice husk biochar to high-density
polyethylene, varying the pyrolysis temperature of the biochar [40]. Ayadi et al. inves-
tigated the effect of pyro-gasification temperature on the mechanical characteristics of
biochar–polymer biocomposites [41].
The aim of this study was to achieve desirable properties of recycled HDPE close
to those of virgin HDPE. For this purpose, particles of rice husk were converted into
biochar. Three types of property were studied, i.e., mechanical, thermal, and fire retardant.
Higher amounts of cellulose and proper dispersion of the rice husk biochar caused an
enhancement in the mechanical properties of the recycled HDPE, whereas the formation
of inorganic substances, and char layers increased the thermal and flame retardancy of
the recycled HDPE. HDPE was found to fill the voids on the rough surfaces of biochar
particles which has caused improvement in the mechanical properties, along with the
improvement in the thermal and fire-retardant properties. Moreover, very little research
has been done on recycled polymers. This works represents an attempt to move the recycled
polymer industry into the limelight, so that more research will be carried out on this topic
in the future.

2. Materials and Methods

Recycled HDPE pellets having a density of 0.96 g/cm3 and melt flow index of
0.55 g/10 min were obtained from NEWTECH pipes, Islamabad, Pakistan. The HDPE
was recycled by the company from faulty pieces of pipe. It is a post-industrial material
obtained from the crushing of HDPE pipes and re-extrusion. Rice husk with a bulk density
of 0.12 g/cm3 was purchased from Allied Industry, Lahore, Pakistan.
Polymers 2023, 15, 1827 4 of 17

The raw rice husk was crushed in a masala grinder (Geepas Masala grinder—RPM
4500) multiple times, to convert it into rice husk powder. The rice husk powder obtained
from this masala grinder was then passed through a sieve of mesh size 50, to obtain a rice
husk powder particle size of less than 300 µm. This rice husk powder was then put through
the process of pyrolysis in a muffle furnace (Thermolyne Benchtop muffle furnace) at a
temperature of 550 ◦ C, in order to produce rice husk biochar. The pyrolysis temperature
was increased from 25 ◦ C (ambient temperature) to 550 ◦ C, at a heating rate of 15 ◦ C/min
and maintained for 3 h under a 20 mL/min nitrogen environment.
The rice husk biochar and recycled HDPE were then dried under sunlight for 24 h.
The recycled HDPE was mixed with rice husk biochar in a high-speed mixer for 30 min,
to obtained the blends. To mix the composite blends, a micro twin-screw extruder (SHJ-
Omega-20, Shanghai, China) with screw outer diameter of 19.8 mm and length/diameter
ratio of 38:1 was used. Both zones of the extruder, i.e., the extruding zone and blending
zone, were operated at 180 ◦ C.
The resulting pellets were then put in a manual injection molding machine, with the
purpose of making the various samples for the mechanical and other types of test. The
temperature of the manual injection molding was set at 185 ◦ C. The percentage of rice husk
biochar that was mixed with recycled HDPE was varied between 10% and 40%. These
percentages with their nomenclature are shown in Table 1.

Table 1. Nomenclature of the samples.

Recycled Pellets Rice Husk Biochar

Sr. No.# Nomenclature
wt. % wt. %
1 100 0 Rec-HDPE
2 90 10 C10
3 80 20 C20
4 70 30 C30
5 60 40 C40

FTIR spectroscopy was carried out, in order to investigate and analyze the pos-
sible interactions between the matrix (Recycled HDPE) and filler (Rice husk biochar).
This was performed with FTIR equipment (Scientific Nicolet 6700 model, Waltham, MA,
USA), using a KBr disc method, with spectra ranging from 500 to 4000 cm−1 (32 scans at
4 cm−1 resolution).
Mechanical characterization of all the samples was performed using tensile, bending,
and impact tests. The tensile test was performed using a Testometric Inc., Manchester,
UK (Load cell: 100 kN), with reference to the D638-14 ASTM standard and a cross-head
speed of 1.5 mm/s. A gauge length of 25 mm was used. The bending test was performed
using a Testometric Inc., UK (Load cell: 100 kN), with reference to the D790-10 ASTM
standard and a cross-head speed of 1.5 mm/s. A span length of 51 mm was used. The
test was a three-point bending test. An Izod impact test was performed using a TM235,
Bangkok, Thailand (Load arm: 16 kg Model) with reference to the D256-10 ASTM standard.
The V-notch in the testing specimens was made using a milling machine (Hermle UWF,
Gosheim, Germany). Mechanical tests were carried out on 5 samples for each composition.
Scanning electron microscopy (SEM) was conducted with a JEOL JSM5910 (Tokyo,
Japan) (maximum magnification: 300,000×; maximum resolving power: 2.3 nm) on spec-
imens that had undergone tensile testing. The dispersion of the filler particles, possible
interactions between the matrix and filler particles, as well as the reasons behind the
variation in tensile properties were observed with a microscope.
The fire retardancy of all composite samples was checked using a horizontal and
vertical burning tests, cone calorimetric tests, and limited oxygen index test (LOI test). Hori-
zontal and vertical burning tests were carried out, in order to investigate the reaction-to-fire
properties according to the UL-94 standards with reference to the D635-03 and D3801-19
ASTM standards. The dimensions of the samples for both tests were 125 × 13 × 3.6 mm.
Polymers 2023, 15, 1827 5 of 17

The composite burning time and rates were determined in a horizontal burning test,
whereas the flame time, afterglow time, extent of after flame or afterglow up to the holding
clamp, and dripping of cotton due to flaming drops for all types of composite specimen
were analyzed in a vertical burning test. After the horizontal burning tests, the com-
posites were awarded an HB rating based on the burning rate, and they were awarded
V-0, V-1, or V-2 on the basis of the abovementioned parameters observed in the verti-
cal burning test. Cone calorimeter (CC) tests were also performed, in order to evaluate
the reaction-to-fire characteristics of the specimens using the E1354-17 ASTM standard.
Samples of 100 × 100 × 3.2 mm were conditioned at 50% relative humidity and 23 ◦ C.
An external heat flux of 50 kW/m2 was used to determine the various flammable prop-
erties. The type of cone calorimeter employed for this purpose was from FTT Limited,
East Grinstead, UK. The limited oxygen index (LOI) of all samples was determined us-
ing an oxygen index tester. The standard ASTM D 2863-17 was followed, with a sample
size of 100 mm × 6.5 mm × 3.2 mm. This was performed in a Sataton Limited oxygen
index tester. The flow rate of oxygen and oxygen–nitrogen mixture were 3 L/min and
20 L/min, respectively.
Thermal stability was investigated in a Perkin Elmer, Waltham, MA, USA (Pyris
Diamond Series TG/DTA model) using TG and DTG curves. This was carried out by
heating the sample at a constant rate in an inert atmosphere. Heating was performed at a
rate of 20 ◦ C/min at a flow rate of 35 mL/min in an inert atmosphere of nitrogen. Weight
loss vs. temperature plots were recorded as a result of the TGA. Similarly, in the case of
DTG, the rate of material loss (weight loss) with heating was plot against the temperature
and used to simplify the readings of the TG curves, which were quite close together.

3. Results
The FTIR spectra of the composite samples, as well as the recycled HDPE and rice husk
biochar, are shown in Figure 1. Different peaks were observed at different wavenumbers,
which are shown in Table 2. However, the intensity of these peaks varied from sample to
sample. C-H stretching vibration, which is attributed to aliphatic structures, was responsi-
ble for the peak at 2924 cm−1 [42]. Similarly, the peak at 1492 cm−1 reflected C-H bending,
which is a sign of alkanes [31]. However, if we focus on the wavenumber 955 cm−1 , peaks
can be observed for the composite samples, but no peak is observed for the recycled HDPE
sample. These peaks in the biochar-derived composite sample were actually caused by
C-O stretching vibration in the composite samples only, which indirectly indicates a lack
of C-O stretching vibration in the recycled HDPE [43]. This reveals that the peak at this
wavenumber was caused by a functional group that is only present in rice husk biochar,
similarly to the presence of carbohydrates only found in rice husk. Similarly, the minor
peak at 3611 cm−1 is related to H2 O, which is caused by O-H bond stretching vibration, and
was weakly detected and only contributed by the biochar [44–47]. The peak at 1614 cm−1
demonstrates C=C stretching [48], whereas that at 778 cm−1 represents the silica functional
group [49]. Both of these groups were also contributed by the rice husk biochar. The above
study also showed that these functional groups were either contributed by the recycled
HDPE or rice husk biochar, without any new functional groups being present. This revealed
the potential of the physical combination of HDPE and rice husk biochar.
Figure 2 compares the tensile properties of the rice husk biochar derived composite
samples with the recycled HDPE. The tensile strength of recycled HDPE was found to be
14.99 MPa. The tensile strengths of C10, C20, C30, and C40 were 15.71, 16.43, 18.54, and
15.97 MPa, respectively. The maximum tensile strength was exhibited by C30. At C30, a 24%
increase in tensile strength was observed, compared to the 14.99 MPa of recycled HDPE.
Regarding the elastic modulus, the elastic modulus of the recycled HDPE was found to
be 1.01 GPa, and the elastic moduli of C10, C20, C30, and C40 were 1.11, 1.18, 1.35, and
1.1 GPa, respectively. The maximum elastic modulus was displayed by C30, which showed
an 34% enhancement in tensile modulus.
 O-H Stretching of Phenolic hydroxyl and Alcohol hy-
C10,C20,C30,C40 3611
droxyl
2924 C-H Stretching of Hydrocarbons
1614 C=C Stretching of Hydroxyl Functional groups
1492 C-H Bending of Alkanes
Polymers 2023, 15, 1827 955 C-O Stretching of Carbohydrates 6 of 17
778 Silicon Hydrogen Single Bond (Si-H)

Figure1.1.FTIR
Figure FTIRof
ofrecycled
recycledHDPE
HDPEand
andall
allcomposites.
composites.

Table With reference

2. Functional to our
groups case,
in the the highand
composites tensile
filler strength
particles, of the 30% ricetohusk
corresponding biochar de-
their wavelength.
rived composite could be attributed to the uniform and homogenous dispersion of biochar
Material Wavelength (cm−1 ) Bonds
in the HDPE matrix, less agglomeration of particles, and a good stress transfer mecha-
Recycled HDPE 2924 C-H Stretching
nism, which was caused by good interfacial bonding, due to proper filling of Hydrocarbons
of the biochar
1492 C-H Bending of Alkanes
pores by the recycled HDPE, which is also shown in the SEM image of C30. With the
O-H Stretching of Phenolic hydroxyl
Rice husk
addition biochar
of 40% 3611
biochar, the tensile strength decreased because of the non-uniform dis-
and Alcohol hydroxyl
persion of biochar particles, greater agglomeration of particles, and of
C=C Stretching weak interfacial
Hydroxyl
Polymers 2023, 15, x FOR PEER REVIEW 1614 7 of 17
Functional groups
955 C-O Stretching of Carbohydrates
778 Silicon Hydrogen Single Bond (Si-H)
O-H Stretching of Phenolic hydroxyl
bonding C10,C20,C30,C40 3611 biochar particles are subject to less defor-
[51]. Regarding the elastic modulus, and Alcohol hydroxyl
mation and are extremely rigid. On account 2924of this property,C-Hthe Stretching
mobility of ofthe recycled
Hydrocarbons
HDPE macromolecules was severely restricted, and this led to C=C
an Stretching
increase in of Hydroxyl
elastic mod-
1614
Functional groups
ulus with the addition of biochar particles to
1492 the recycled HDPE, from 0 to 30% [52].
C-H Bending of Alkanes
The
elastic modulus of the C40 might have been 955low due to the agglomeration
C-O Stretchingofofparticles and
Carbohydrates
778 and matrix.Silicon
poor stress transfer between the filler particles The SEMHydrogen
imagesSingle
furtherBond (Si-H)
illus-
trate the causes of the variation in the tensile properties.

Figure
Figure2.2.Tensile
Tensileproperties of of
properties thethe
recycled HDPE
recycled andand
HDPE composites.
composites.

SEM images of the tensile cross-sectional fracture surface of the recycled HDPE, as
well as the rice husk biochar composites, are shown in Figure 3. The smooth structure of
recycled HDPE is shown in Figure 3a. For the 30% rice husk reinforced composite, i.e., in
the case of C30, the porous structure of biochar was evident, as can be seen in Figure 3b.
 HDPE macromolecules was severely restricted, and this led to an increase in elastic mod-
ulus with the addition of biochar particles to the recycled HDPE, from 0 to 30% [52]. The
elastic modulus of the C40 might have been low due to the agglomeration of particles and
poor stress transfer between the filler particles and matrix. The SEM images further illus-
Polymers 2023, 15, 1827 trate the causes of the variation in the tensile properties. 7 of 17

The mechanical properties of composites are dependent on the homogeneous disper-

sion of filler particles in the matrix and the extent of agglomeration of the particles with each
other. Another factor that reflects the tensile strength of a composite is the stress transfer
mechanism of interfacial bonding [50]. If the recycled HDPE uniformly and effectively
filled the pores of the biochar and transferred the stress productively, then the chance of an
increase in mechanical properties was extremely high, as this would provide rigidity to
the composite.
With reference to our case, the high tensile strength of the 30% rice husk biochar de-
rived composite could be attributed to the uniform and homogenous dispersion of biochar
in the HDPE matrix, less agglomeration of particles, and a good stress transfer mechanism,
which was caused by good interfacial bonding, due to proper filling of the biochar pores by
the recycled HDPE, which is also shown in the SEM image of C30. With the addition of 40%
biochar, the tensile strength decreased because of the non-uniform dispersion of biochar
particles, greater agglomeration of particles, and weak interfacial bonding [51]. Regarding
the elastic modulus, biochar particles are subject to less deformation and are extremely
Figure
rigid. 2. Tensile
On accountproperties
of thisofproperty,
the recycledtheHDPE and composites.
mobility of the recycled HDPE macromolecules
was severely restricted, and this led to an increase in elastic modulus with the addition
SEM images
of biochar particles of to
the
thetensile cross-sectional
recycled HDPE, fromfracture
0 to 30% surface of the
[52]. The recycled
elastic modulusHDPE, as
of the
well as the rice
C40 might havehuskbeenbiochar
low due composites, are shown in
to the agglomeration ofFigure 3. The
particles and smooth structure
poor stress of
transfer
recycled
between HDPE is particles
the filler shown inand Figure 3a. For
matrix. Thethe
SEM30% rice husk
images reinforced
further illustratecomposite,
the causesi.e., in
of the
the case ofinC30,
variation the porous
the tensile structure of biochar was evident, as can be seen in Figure 3b.
properties.
MostSEM of theimages
pores of the tensile
biocharcross-sectional
were uniformly filled by
fracture the recycled
surface HDPE. The
of the recycled HDPE,better
as
distribution
well as the rice of the filler
husk particles
biochar can be viewed
composites, in this figure.
are shown This
in Figure 3.led
Thetosmooth
a good physical–
structure
of recycled interlocking
mechanical HDPE is shown in Figure
structure 3a. This
[44–46]. For the 30% rice
superior husk reinforced
dispersion also caused composite,
an effi-
i.e., in
cient the case
transfer of of C30,between
stress the porous structure
the rice of biochar
husk biochar was evident,
particles as canHDPE.
and recycled be seenThisin
Figure 3b. Most
phenomenon of the that
revealed pores theofhighest
the biochar were
tensile uniformly
strength amongfilled by the recycled
all samples HDPE.
was for C30. In
TheSEM
the better distribution
image of C40 in of Figure
the filler3c,particles
there are can be viewed
some signs ofinagglomeration
this figure. This andledclusters
to a good
of
physical–mechanical interlocking structure
rice husk biochar, which lowered the tensile strength. [44–46]. This superior dispersion also caused
an efficient transferC30
Furthermore, of stress between the rice
also displayed husk
highest biochar
tensile particles
modulus, and
due torecycled
the havingHDPE.
the
This phenomenon
most interlocking revealed
of biochar that the highest
pores with the tensile strength
recycled HDPE,amongwhichall samples was for and
gave it rigidity C30.
In the SEM
stiffness. C10 image of C40the
displayed in lowest
Figure tensile
3c, there are someowing
modulus, signs to
of the
agglomeration
lower rice husk and biochar
clusters
of rice husk biochar, which lowered the tensile strength.
loading, whereas the agglomeration in C40 also caused a decreased tensile modulus.

Figure 3. SEM images of (a) unmodified recycled HDPE, (b) 30% rice husk reinforced recycled HDPE,
and (c) 40% rice husk reinforced recycled HDPE.

Furthermore, C30 also displayed the highest tensile modulus, due to the having the
most interlocking of biochar pores with the recycled HDPE, which gave it rigidity and
stiffness. C10 displayed the lowest tensile modulus, owing to the lower rice husk biochar
loading, whereas the agglomeration in C40 also caused a decreased tensile modulus.
Figure 4 compares the flexural properties of the recycled HDPE with the biochar-
derived composite samples. The flexural property of the recycled HDPE was discovered to
 ties was found to be similar to that of the tensile properties.
This enhancement in flexural properties was due to the porous structure of the bio-
char and the physical interlocking between the biochar and recycled HDPE. When screw
extrusion was performed, the HDPE (which was in a fluid state) could fill the pores of the
Polymers 2023, 15, 1827 biochar, so that a rigid structure with a good interaction between them was achieved;8and of 17
after cooling, a strong physically interlocking structure was secured [11].This was the
main reason behind the enhancement in the flexural properties with the addition of bio-
char to theMPa.
be 20.12 recycled
The HDPE,
flexuralsince it allowed
properties transferring
of C10, C20, C30,the
and stress
C40efficiently.
were 20.56,Another fac-
21.94, 23.91,
tor responsible for the variation in the flexural properties, and reported
and 22.12 MPa, respectively. C30 demonstrated an enhancement of 19% in flexural strengthin many docu-
ments, waswith
compared the good particleHDPE
the recycled dispersion in the matrix
and showed [53,54]. flexural
the maximum This could also have
strength. been
Moreover,
the
C30reason behind the
also recorded decreaseofin80%
an increase thefor
flexural strength
the flexural and flexural
modulus comparedmodulus in the
with the C40
recycled
composite.
HDPE, which Thedisplayed
biochar particles
a 0.77 GPamay not have
flexural been uniformly
modulus. C10, C20, dispersed
C30, and C40in the HDPE
displayed
matrix or these
0.99, 1.14, 1.39,particles
and 1.09might
GPa have become
flexural moduli.agglomerated,
The trend inas the
a result of which
flexural there was
properties was
appreciable reduction in the flexural characteristics.
found to be similar to that of the tensile properties.

Figure
Figure4.4.Flexural
Flexuralproperties
propertiesofofthe
therecycled
recycledHDPE
HDPEand
andcomposites.
composites.

Thisimpact
The enhancement in flexural
strengths properties
of the recycled was due
HDPE andtocomposite
the porousmaterials
structureareof the biochar
shown in
and the
Figure 5. physical
The impactinterlocking
strength of between the biochar
the recycled HDPE,and recycled
C10, C20, C30,HDPE.and When screw
C40 were ex-
3.43,
trusion was performed, the HDPE (which was in a fluid state) could fill
3.77, 5.76, 5.11, and 4.51 KJ/m , respectively. The impact strengths all displayed a different
2 the pores of the
biochar,
trend so that atorigid
compared structure
the tensile with a and
strength goodflexural
interaction between
strength. them waswas
Its decrease achieved; and
consistent
after cooling, a strong physically interlocking structure was secured [11].This
with the fiber–polymer composites [18,55]. The decrease of the impact strength from the was the main
reason behind
rec-HDPE to thethe
C40enhancement
sample was aroundin the flexural
22.5%. properties with the addition of biochar
to the recycled HDPE, since it allowed transferring
The impact strength of a composite material is entirely the stress efficiently.
dependent on theAnother
rigidityfactor
and
responsible for the variation in the flexural properties, and reported in
toughness [31]. The lesser the rigidity of the material, the greater its toughness, and the many documents,
was theits
greater good particle
impact dispersion
strength, and vicein the matrix
versa. The[53,54].
rigidityThis could
of the also have
materials wasbeen the reason
dependent on
behind the decrease in the flexural strength and flexural modulus
the mobility of the recycled HDPE molecules, which in turn was dependent on the phys- in the C40 composite.
The biochar particles
ical–mechanical may notstructure
interlocking have been uniformly
of the biochardispersed in the HDPE
with the HDPE matrix
molecules. or these
When the
particles might have become agglomerated, as a result of which there was appreciable
reduction in the flexural characteristics.
The impact strengths of the recycled HDPE and composite materials are shown in
Figure 5. The impact strength of the recycled HDPE, C10, C20, C30, and C40 were 3.43,
3.77, 5.76, 5.11, and 4.51 KJ/m2 , respectively. The impact strengths all displayed a different
trend compared to the tensile strength and flexural strength. Its decrease was consistent
with the fiber–polymer composites [18,55]. The decrease of the impact strength from the
rec-HDPE to the C40 sample was around 22.5%.
 20% to 40%, the recycled HDPE started filling the pores of the biochar and the ability of
the recycled HDPE to move began to be limited. This caused the increase in the rigidity of
the composite and decrease in the impact strength of the samples [31]. As such, less energy
was required to resist a sudden impact as the content was increased to 40%. Hence, the
impact energy started to decrease. Another reason might have been that there were abun-
Polymers 2023, 15, 1827 9 of 17
dant regions of poor stress concentrations, and this led to easier crack propagation in the
composite samples [31]. Table 3 compares the mechanical properties of the samples.

Figure 5. Impact properties of the recycled HDPE and

and composites.
composites.

TableThe impact strength

3. Mechanical of aofcomposite
properties the recycled material
HDPE and is entirely dependent on the rigidity and
composites.
toughness [31]. The lesser the rigidity of the material, the greater its toughness, and the
Tensile Impact
greater its impact strength, and vice
Tensile versa. The
Modu- rigidity ofFlexural
Flexural the materials
Modu-was dependent
Samples Strength
on the mobility of the recycled HDPE molecules, which in turn Strength
was dependent on the
lus (GPa) Strength (MPa) lus (GPa)
(MPa)interlocking structure of the biochar with the HDPE molecules.
physical–mechanical (kJ/mWhen
2)

theRec-
content of the rice husk biochar
14.99 1.01 in the recycled20.12HDPE matrix0.77 was 10%, there3.43 was less
HDPEof the recycled HDPE flowing into the pores of biochar, and thus the mobility of the
chance
C10 HDPE 15.71
recycled was very high. Its 1.11
ability to absorb 20.56
energy during 0.99 fracture propagation 3.77 was
excellent,
C20 and thus 16.43 its toughness1.18was high. There were less regions
21.94 1.14of stress concentration,
5.76
which
C30required 18.54
less energy to induce
1.35 cracks in the composite, and1.39
23.91 thus the impact5.11 strength
wasC40
very high. However,
15.97 as the content
1.10 of rice husk
22.12biochar was increased
1.09 from 20% to 40%,
4.51
the recycled HDPE started filling the pores of the biochar and the ability of the recycled
HDPE to move began
Horizontal to be limited.
and vertical burning This caused
tests werethe increaseon
conducted in the rigidity of the
all specimens, i.e.,composite
with and
and decrease in the impact strength of the samples [31]. As such, less
without the inclusion of the rice husk biochar in the recycled HDPE. The results were energy was required
then
to resist a sudden impact as the content was increased to 40%. Hence,
compared with the UL-94 standard for horizontal and vertical burning tests. For both the the impact energy
started to specimens
tests, five decrease. Another reason were
for each sample mighttested,
have and
beenthethat there of
average were
the abundant
results wasregions
taken.
of poor stress concentrations, and this led to easier crack propagation
In the case of the horizontal burning test, the time needed to reach from 25 in mm
the composite
to 100 mm
samples
(burning[31]. Table
time) was3increased
comparesas thethe
mechanical
content ofproperties
rice huskofbiochar
the samples.
in the recycled HDPE
was increased. This caused a decrease in the burning rate from the recycled HDPE to C40.
Table 3. Mechanical properties of the recycled HDPE and composites.
All the specimens received an HB rating based on the burning rate, except the recycled
HDPE sample, whose burning rate
Tensile was greater Flexural
Tensile than 40 mm/min and, thus, not
Flexural awarded
Impact
an HB rating. TheStrength
Samples decrease in the average burning
Modulus rate from Modulus
Strength the recycled HDPE (45.10
Strength
(MPa)
mm/min) to C40 (25.99 (GPa)
mm/min) was 42.37%. (MPa) (GPa) (kJ/m2 )
Rec-HDPE 14.99 1.01 20.12 0.77 3.43
C10 15.71 1.11 20.56 0.99 3.77
C20 16.43 1.18 21.94 1.14 5.76
C30 18.54 1.35 23.91 1.39 5.11
C40 15.97 1.10 22.12 1.09 4.51

Horizontal and vertical burning tests were conducted on all specimens, i.e., with and
without the inclusion of the rice husk biochar in the recycled HDPE. The results were then
compared with the UL-94 standard for horizontal and vertical burning tests. For both the
tests, five specimens for each sample were tested, and the average of the results was taken.
In the case of the horizontal burning test, the time needed to reach from 25 mm to 100 mm
(burning time) was increased as the content of rice husk biochar in the recycled HDPE was
increased. This caused a decrease in the burning rate from the recycled HDPE to C40. All
the specimens received an HB rating based on the burning rate, except the recycled HDPE
Polymers 2023, 15, 1827 10 of 17

sample, whose burning rate was greater than 40 mm/min and, thus, not awarded an HB
rating. The decrease in the average burning rate from the recycled HDPE (45.10 mm/min)
to C40 (25.99 mm/min) was 42.37%.
In the case of the vertical burning test, the flame and afterglow times after the 1st and
2nd flame applications progressively decreased with the increase in the biochar loading,
from C20 to C40. This was why the recycled HDPE did not receive a rating, due to its
poor flame retardancy characteristics. C10 also did not obtain a rating, due to the small
amount of biochar. The after-flame time for C10 was greater than for the recycled HDPE,
because the content of biochar was less. The rice husk biochar partially slowed down the
flame speed but could not stop it, and the flame eventually reached the holding clamp. C20
obtained the rating of V-2, owing to the relatively high content of biochar, which resisted
the flame and did not allow it to reach the holding clamp. C30 and C40 obtained a V-1
rating, owing to the shorter after flame and afterglow times, during which the rice husk
biochar acted against the flame, slowed down the process of combustion, and stopped the
flame before it reached the holding clamp. Cotton dripping was also not recorded with the
C20, C30, and C40 samples. Finally, C40 had the lowest chance of burning. It is expected
that, following this trend, recycled HDPE having 50% biochar would achieve a rating of
V-0. Table 4 compares the fire-retardant properties of all samples.

Table 4. Fire retardant properties of the recycled HDPE and composites.

LOI
Cone Calorimetric Test Horizontal Burning Test Vertical Burning Test
Test

Max After Flame + After Glow Time(s)

Avg. Burning Rate (mm/min)

Flame up to the Holding Clamp

Cotton Ignited by Flaming Drops

Avg. Burning Time (min)

Max. After Flame Time (s)

Total After Flame Time (s)

Material Types

TTI (s)

TPHRR (s)

PHRR (kW/m2 )

THR (MJ/m2 )

Rating

Rating

LOI (%)

Rec-HDPE 59 210 633 144 1.66 45.10 Nil 61 281 - Yes Yes Nil 16.97
C10 32 214 434 120 2.01 37.19 HB 63 304 - Yes Yes Nil 18.82
C20 28 222 399 103 2.30 32.66 HB 26 235 34 No Yes V-2 20.73
C30 30 229 344 83 2.64 28.38 HB 16 152 22 No No V-1 23.01
C40 31 233 301 68 2.89 25.99 HB 7 59 8 No No V-1 25.28

Cone calorimeter tests were performed for the purpose of elaborating the principal
fire retardant characteristics of the recycled HDPE, as well as the rice husk biochar derived
composite samples. Figures 6 and 7 show the HRR and THR curves of all samples with the
response time, whereas Table 4 displays the time to ignition (TTI), time to peak heat release
rate (TPHRR), heat release rate (HRR), and total heat release rate (THR) of all samples.
Polymers 2023, 15,
Polymers 2023, 15, 1827
x FOR PEER REVIEW 11of
11 of 17
17
Polymers 2023, 15, x FOR PEER REVIEW 11 of 17

Figure 6.
6. Heat release rate of
of the recycled
recycled HDPE and
and composites.
Figure 6. Heat
Figure Heat release
release rate
rate of the
the recycled HDPE
HDPE and composites.
composites.

Figure 7. Total heat release rate of the recycled HDPE and composites.
Figure 7.
Figure 7. Total
Total heat
heat release
release rate
rate of
of the
the recycled
recycledHDPE
HDPEand
andcomposites.
composites.
Limited oxygen index (LOI) tests were performed, for the purpose of elaborating and
Limited
Time oxygen index
to ignition (TTI) is(LOI)
one tests
of thewere performed,
crucial factors that for the purpose
dictates of elaborating
the flammable and
charac-
further characterizing the flame retardancy behavior of the recycled HDPE as well as the
further characterizing
teristics of composites.the Theflame retardancy
recycled HDPE behavior
took someoftime the recycled
to ignite HDPE
and catchas well as the
fire (59 s),
biochar-derived composite samples. The greater the LOI of a specimen, the better its flame
whereas the TTI of
biochar-derived the rice husk
composite biochar
samples. The derived
greater the samples
LOI offirst decreased
a specimen, for
the C10 and
better C20
its flame
retardant properties. The limited oxygen index basically refers to the volume ratio of ox-
and then increased
retardant properties.forThe
C30limited
and C40oxygen
as the content of the biochar
index basically refersincreased.
to the volumeThis ratio
means ofthat
ox-
ygen in a mixture of nitrogen and oxygen. It is the minimum concentration of oxygen that
the rice husk biochar samples were ignited in less time compared
ygen in a mixture of nitrogen and oxygen. It is the minimum concentration of oxygen that to the recycled HDPE.
is required to sustain a flame or to support the combustion of a material.
This decrease
is required in TTI was
to sustain immediate
a flame when the biochar
or to support combustion was of added to the composites, i.e.,
a material.
With reference to the LOI of the recycled HDPE and the biochar-derived samples, as
from With
the recycled
referenceHDPEto thetoLOIC10. This
of the decrease
recycled HDPEin TTI andwith
the the addition of biochar
biochar-derived samples, was
as
shown in Figure 8, the LOI of the recycled HDPE was the lowest, whereas it increased as
consistent with the
shown in Figure 8,report
the LOIof of
Dastheetrecycled
al. [11]. Similarly,
HDPE was thethe
peak heat release
lowest, whereas rate (PHRR) and
it increased as
the content of rice husk biochar in the composite samples was increased.
total heat release rate (THR) are also critical factors in
the content of rice husk biochar in the composite samples was increased. judging the fire-retardant characteris-
tics ofThe
The
recycled HDPE
composites
recycled HDPE
showedthe
and describe
showed the
theoverall
LOI ofcombustion
16.97%, whereas
LOI of 16.97%, whereas behaviorthe LOI
the of
LOI theofmaterial
C40 was 25.28%,
of C40 was[56]. On
25.28%,
which
the otherwas highest
hand, among
TPHRR all
tells ussamples.
about This
the time trend
it of
takes the
to enhancement
produce the in LOI
maximum is amount
consistent of
which was highest among all samples. This trend of the enhancement in LOI is consistent
with previous
heat. The peak reports
heat [44–46].
release rateThis means
(PHRR) andthat an increase
total heat of 48.97%
release rate was recorded
(THR) of the in the
recycled
with previous reports [44–46]. This means that an increase of 48.97% was recorded in the
LOI from
HDPE werethehighest
recycled HDPE
at 633 kW/m to C40.
2 and The
144prime
MJ/mreason 2 , due to behind
its poorthisflammable
was the presence
properties of
LOI from the recycled HDPE to C40. The prime reason behind this was the presence of
biochar,
and the which
intense enhanced
combustion, the flame-retardant
whereas both of properties
these of
properties the composites.
showed a Biochar
decline with has a
the
biochar, which enhanced the flame-retardant properties of the composites. Biochar has a
very high thermal stability, so inclusion of biochar repelled the heat transport between the
very high thermal stability, so inclusion of biochar repelled the heat transport between the
Polymers 2023, 15, 1827 12 of 17

addition of rice husk biochar to the composite samples, with the 40% rice husk biochar
derived composite sample displaying the lowest PHRR (301 kW/m2 ) and lowest THR
(68 MJ/m2 ).
This meant that C40 exhibited a large decrease of 52.40% in PHRR value and 52.88%
in THR value. C40 also had the longest TPHRR (233 s) among all samples, which is also
a positive attribute. All these desirable shifts in properties occurred with the increase in
the content of biochar in the composite samples. This means that C40 displayed the best
flammable properties, and the trend in best fire-retardant properties was as follows:

C40 > C30 > C20 > C10 > Recycled HDPE

The presence of biochar, which also possessed excellent thermal properties, acted as a
hindering agent and became a barrier to the transfer of heat between the recycled HDPE
and the source of heat [11,17]. Moreover, the formation of char layers from the rice husk
biochar played a pivotal role in reducing the HRR and PHRR values [11].
Limited oxygen index (LOI) tests were performed, for the purpose of elaborating
and further characterizing the flame retardancy behavior of the recycled HDPE as well as
Polymers 2023, 15, x FOR PEER REVIEW
the biochar-derived composite samples. The greater the LOI of a specimen, the better 12 ofits
17
flame retardant properties. The limited oxygen index basically refers to the volume ratio of
oxygen in a mixture of nitrogen and oxygen. It is the minimum concentration of oxygen
that is required
source to sustain
of heat and a flameHDPE
the recycled or to support thealso
[11]. It was combustion
reportedofinathe
material.
literature that, dur-
With
ing the reference
process to the LOI
of pyrolysis or of the recycled many
carbonization, HDPEmetal
and the biochar-derived
oxides and inorganicsamples, as
substances
shown in Figure 8, the LOI of the recycled HDPE was the lowest, whereas
are formed, which have the ability to slow down the process of combustion, as they areit increased as
the content of rice
nonflammable husk biochar in the composite samples was increased.
[57–59].

Figure8.8.Limited
Figure Limitedoxygen
oxygenindex
indexof
ofthe
therecycled
recycledHDPE
HDPEand
andcomposites.
composites.

Table 4. Fire
The retardant
recycled HDPEproperties
showed of the
the recycled HDPE and
LOI of 16.97%, composites.
whereas the LOI of C40 was 25.28%,
which was highest among all samples. This trend of the enhancement in LOI is consistent
Cone Calorimetric LOI
with previous Horizontal BurningThis
reports [44–46]. Test means that an increase
Vertical Burningwas
of 48.97% Testrecorded in the
Test Test
Material Types

LOI from the recycled HDPE to C40. The prime reason behind this was the presence of
Avg. Burning Time

Avg. Burning Rate

Max After Flame +

Cotton Ignited by
Total After Flame
Max. After Flame

After Glow Time

Holding Clamp
Flame up to the

biochar, which enhanced the flame-retardant properties of the composites. Biochar has a
PHRR (kW/m2)

Flaming Drops
THR (MJ/m2)
TPHRR (sec)

(mm/min)

very high thermal stability, so inclusion of biochar repelled the heat transport between the
Time (s)

Time (s)

LOI (%)
TTI (s)

Rating

Rating
(min)

source of heat and the recycled HDPE [11]. It was also reported in the literature that, during
(s)

the process of pyrolysis or carbonization, many metal oxides and inorganic substances
are formed, which have the ability to slow down the process of combustion, as they are
nonflammable [57–59].
Rec-HDPE 59 210 633 144 1.66 45.10 Nil 61 281 - Yes Yes Nil 16.97
C10 32 214 434 120 2.01 37.19 HB 63 304 - Yes Yes Nil 18.82
C20 28 222 399 103 2.30 32.66 HB 26 235 34 No Yes V-2 20.73
C30 30 229 344 83 2.64 28.38 HB 16 152 22 No No V-1 23.01
C40 31 233 301 68 2.89 25.99 HB 7 59 8 No No V-1 25.28
Polymers 2023, 15, 1827 13 of 17

Thermogravimetric and derivative thermogravimetric curves are shown in

Figures 9 and 10. The TG curves depict the percentage weight loss of the samples, whereas
the DTG displays the derivative of those curves. These curves show that, as the heating
temperature was increased, the samples initially responded well, with no degradation,
but as the temperature reached 402.34 ◦ C, the recycled HDPE sample started to thermally
degrade, with degradation occurring at 522.16 ◦ C. As the heating temperature was further
increased, all samples started to degrade one by one, with C40 degraded last. We can
also notice from the TGA that, as the biochar content in the composite samples was in-
creased, the delay in thermal degradation increased, and this delay increased as the biochar
content in the recycled HDPE was increased. This means that the increase in the biochar
loading was extremely important in repelling the heat from decomposing the composite
samples and in increasing the time of decomposition. In addition, the onset degradation
temperature (T0 ) also rose with the increase in rice husk biochar loading. This increase was
recorded as 4.05% from the recycled HDPE (425.09 ◦ C) to C40 (442.36 ◦ C). Table 5 shows the
onset degradation temperature (T0 ), start degradation temperature (T1 ), finish degradation
temperature (T2 ), point of inflection temperature (Tpeak ), and residue % at 600 ◦ C.

Figure 9. TG curves of the recycled HDPE and composites.

Figure 10. DTG curves of the recycled HDPE and composites.

Polymers 2023, 15, 1827 14 of 17

Table 5. Thermal properties of the recycled HDPE and composites.

T0 (Onset T1 (Start T2 (Finish Tpeak (Point of

Type of Sample Degradation Degradation Degradation Inflection Residue % at 600 ◦ C
Temperature) (◦ C) Temperature) (◦ C) Temperature) (◦ C) Temperature) (◦ C)
Rec-HDPE 425.09 402.34 522.12 459.63 0.39%
C10 435.86 406.12 528.05 466.41 10.95%
C20 440.93 410.87 535.67 471.18 21.47%
C30 438.14 416.03 541.31 477.35 32.09%
C40 442.36 421.21 548.88 481.22 43.51%

Moreover, if we look at the TG curves, we come to the conclusion that the amount of
residue left after heating was directly proportional to the biochar loading. Das reported
that this increase in residue generation is due to the increase in stable biochar loading [11].
De Bhowmick et al. also reported that the main reason behind the increase in the residue is
the enrichment of stable SiO2 in stable biochar loading [57]. This is why the recycled HDPE
was almost completely decomposed after heating and why this decomposition decreased
as we moved towards higher loadings of biochar. C40 retained the maximum residue after
heating, owing to a greater percentage of biochar. This increase in residues at 600 ◦ C also
proved the fact that the thermal stability was improved with the addition of biochar. The
following trend of residue retention was followed by the samples:

C40 > C30 > C20 > C10 > Recycled HDPE

Hence, we come to the conclusion that biochar is an extremely important additive for
increasing the thermal stability of composites.

4. Conclusions
The influence of variation of the rice husk biochar content in recycled HDPE was
evaluated, in order to maximize the use of agricultural waste. All functional groups were
supplied either by the recycled HDPE or rice husk biochar, which was revealed using FTIR.
The 30% biochar loading had the highest tensile strength (18.54 MPa), tensile modulus
(1.35 GPa), flexural strength (23.91 MPa), and flexural modulus (1.39 GPa). The tensile
and flexural strength were increased by 24% and 19%, respectively, compared with the
recycled HDPE, whereas the tensile and flexural moduli were improved by 34% and 80%,
respectively. However, the impact strength decreased (22.5%) when adding rice husk
biochar to the recycled HDPE, due to the increase in rigidity of the composites compared
with the recycled HDPE (4.63 KJ/m2 ). This variation in properties was due to the extent of
agglomeration, level of homogeneous dispersion of the filler particles in the matrix, and
the extent of the recycled HDPE filling the pores of the rice husk biochar, which was also
displayed in the SEM images. Overall, this revealed that the addition of rice husk biochar
had a positive effect on the mechanical properties of the composites.
With the increase in the content of rice husk biochar, the delay in thermal decomposi-
tion was enhanced, the ability to repel the heat from decomposing the composite samples
was increased, and the time of decomposition was also increased. The C40 composite with
40% rice husk biochar displayed the best thermal stability and longest thermal decay time
among all samples. Moreover, C40 showed an increase of 4.05% in the temperature of the
onset of degradation compared to the recycled HDPE.
The composite with 40% rice husk biochar demonstrated the best flame retardancy
characteristics. The horizontal burning test revealed a decrease in the burning rate of the
recycled HDPE from 45.10 mm/min to 25.99 mm/min for C40. The vertical burning test
also showed a change in the flammability rating, from the no rating of recycled HDPE to
the V-1 of C40. The limited oxygen tests also showed that C40 had the highest LOI (25.28%).
Moreover, the cone calorimetry also showed a decrease of 52.40% for the PHRR value
and 52.88% for the THR value compared with the recycled HDPE. This was due to the
Polymers 2023, 15, 1827 15 of 17

inherent capacity of biochar to halt the transport of heat from the heat source to the matrix,
as well as due to the formation of inflammable metal oxides and inorganic substances
during pyrolysis.

Author Contributions: Conceptualization, A.u.R.S., A.I. and A.S.; methodology, A.u.R.S., A.I. and
A.S.; software, A.u.R.S., A.I. and A.S.; formal analysis, A.u.R.S., A.I. and A.S.; investigation, A.u.R.S.,
A.I. and A.S.; writing—original draft preparation, A.u.R.S., A.I., A.S., R.A.M., H.A. and I.A.B.;
writing—review and editing, R.A.M., H.A. and I.A.B.; supervision, A.u.R.S. and H.A. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by Deputyship for Research & Innovation, Ministry of Education
in Saudi Arabia through project number IFPSAU-2021/01/18816.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data are included in the manuscript.
Acknowledgments: The authors extend their appreciation to the Deputyship for Research & Innova-
tion, Ministry of Education in Saudi Arabia for funding this research work through project number
IFPSAU-2021/01/18816.
Conflicts of Interest: The authors declare no conflict of interest.

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