polymers

Review
Enhancing the Potential of Polymer Composites Using Biochar
as a Filler: A Review
Mohamed Aboughaly , Amin Babaei-Ghazvini , Piyali Dhar, Ravi Patel and Bishnu Acharya *

Department of Chemical and Biological Engineering, University of Saskatchewan, 57 Campus Drive,

Saskatoon, SK S7N 5A9, Canada; [email protected] (M.A.); [email protected] (A.B.-G.);
[email protected] (P.D.); [email protected] (R.P.)
* Correspondence: [email protected]

Abstract: This article discusses the scope biochar’s uses; biochar is a sustainable organic material, rich
in carbon, that can be synthesized from various types of biomass feedstock using thermochemical
reactions such as pyrolysis or carbonization. Biochar is an eco-friendly filler material that can enhance
polymer composites’ mechanical, thermal, and electrical performances. In comparison to three
inorganic fillers, namely carbon black, carbon nanotubes (CNT), and carbon filaments, this paper
explores the optimal operating conditions for regulating biochar’s physical characteristics, including
pore size, macro- and microporosity, and mechanical, thermal, and electrical properties. Additionally,
this article presents a comparative analysis of biochar yield from various thermochemical processes.
Moreover, the review examines how the surface functionality, surface area, and particle size of
biochar can influence its mechanical and electrical performance as a filler material in polymer
composites at different biochar loads. The study showcases the outstanding properties of biochar
and recommends optimal loads that can improve the mechanical, thermal, and electrical properties
of polymer composites.

Keywords: biochar; carbonaceous fillers; polymer properties; carbonization; pyrolysis; carbonization

Citation: Aboughaly, M.;

Babaei-Ghazvini, A.; Dhar, P.; Patel, 1. Introduction
R.; Acharya, B. Enhancing the The global polymer industry’s annual value is estimated to reach USD 600 billion [1].
Potential of Polymer Composites The projected growth rate of the industry is expected to contribute towards the accumula-
Using Biochar as a Filler: A Review. tion of 12,000 Mt of plastic wastes in landfills by 2050 [2]. This would negatively impact the
Polymers 2023, 15, 3981. https:// natural environment. The development of polymer composites with bio-based additives is
doi.org/10.3390/polym15193981 essential to mitigate the impact of the use of non-renewable petroleum-based materials on
Academic Editor: the environment. There is a growing demand for polymer composites with improved prop-
Łukasz Klapiszewski erties, such as density, stiffness, strength, and lower cost, due to their various applications
in many industries, including the aerospace, automotive, packaging, and pharmaceutical
Received: 6 September 2023
industries. Thermoplastic polymer composites form 23% of global matrix composites due
Revised: 23 September 2023
to their ability for reheating, re-melting, and reshaping. Thermoset polymer composites
Accepted: 28 September 2023
are the most common due to their great flexibility in product designs, improved structural
Published: 3 October 2023
integrity, and molding ability with different tolerances. However, these composites may
suffer from drawbacks such as low ductility, high voids, limited thermal stability, and
low flame retardancy. The addition of various fillers to polymer composites can help to
Copyright: © 2023 by the authors. overcome these limitations [1]. Biochar is a promising, environmentally friendly, low-
Licensee MDPI, Basel, Switzerland. cost, and sustainable filler material [2–5] which is produced from biomass pyrolysis or
This article is an open access article carbonization. It outperforms traditional fillers such as carbon black, carbon nanotubes,
distributed under the terms and and carbon filaments. Biochar has certain properties, such as high hydrophobicity, which
conditions of the Creative Commons improve its compatibility with the polymer matrix and render a higher thermal stability
Attribution (CC BY) license (https:// compared to alternative filler materials [2–4]. This paper highlights the impact of biochar
creativecommons.org/licenses/by/ at different loads on the mechanical, electrical, and thermal performances of polymer
4.0/).

Polymers 2023, 15, 3981. https://doi.org/10.3390/polym15193981 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 3981 2 of 32

composites. A comparison is made between different carbon-based materials as fillers in

polymer composites [3–5].

2. Production, Properties, and Potential Applications of Biochar in Composites

Lignocellulosic biomass, an abundant and renewable resource, is mainly composed of
cellulose, hemicellulose, and lignin. It is a promising alternative to fossil resources and a
potential feedstock for producing biofuels, bio-based chemicals, and materials including
biochar [6]. Lignocellulosic materials are found in all vascular plants, commonly between
and within the cells, as well as within the cell walls. Biochar is synthesized from biomass
via thermochemical processes such as pyrolysis, carbonization, and gasification [7,8].
During carbonization and pyrolysis, biomass is thermally decomposed at different
heating rates and residence times. The carbonization process involves longer residence
times (24 h) and lower heating rates (1–9 ◦ C/min) [9]. Pyrolysis is a thermal decomposition
reaction that occurs in the complete absence of oxygen and yields products such as solid
char, liquid, and gaseous hydrocarbon fuels [10,11]. The slow pyrolysis process produces
between 15 and 40 wt.% [9,12,13]. The carbonization process occurs between 250 ◦ C and
350 ◦ C and enables the production of a higher product yield of up to 60 wt.% [12–15]. The
most influential factors for biochar quality are the type of biomass feedstock, lignocellulosic
composition, and the operating conditions of pyrolysis. The temperature profile and heat-
ing rate of pyrolysis affect the physicochemical properties of biochar, including its porosity,
pore size, surface area, and tensile strength. These operating conditions also affect the
stiffness and water retention capacity of biochar [16,17]. The physical structure of biochar
is presented in Figure 1 [14–19]. Modifying the structure of biochar greatly affects the filler
properties in polymer composites. Its low molecular density makes it a sustainable replace-
ment for various inorganic fillers in polymer composites, such as glass, silica, and silicon
dioxide. With calibration, additional properties such as electrical conductivity can also
be introduced [19]. The electrical conductivity of biochar increases with higher pyrolysis
operating temperatures due to changes in its microstructure [10,20–23]. Biochar can be
used as a filler material in thermosets, thermoplastic, and ceramic polymer composites to
improve their mechanical, thermal, and electrical properties. Figure 2 shows the statistics
of different fillers which are currently being used in polymer composites.
The shape of fillers affects the filler weight content which typically falls between
25 wt.% and 60 wt.%, while composites with round particles have the highest filler con-
tents [7,15]. Polymer composites with round filler particles achieve higher filler volumes
of up to 60 wt.%, while other filler shapes have lower volumes (25–50% by filler vol-
ume) [19,24].
The addition of reinforcing fillers in polymer composites improves polymer process-
ing, increases stiffness, and raises the heat distortion temperature, which measures the
polymer’s resistance to alteration, and improves creep resistance; additionally, it improves
the abrasion, tear strength, and flame retardancy characteristics [2,7,15]. Enforcement of
biochar in polymer composites has shown improvement in tensile strength, creep resis-
tance, an improvement on anti-stress relaxation in HDPE by enforcement of biochar at
high loads between 50 wt.% and 60 wt.% added composites, as well as maintaining good
dispersion and good mechanical structure [12,25,26]. The enforced polymer composite
achieved flexural strength of more than 30 MPa, a flexural modulus of up to 1.80 GPa,
high tensile strength above 25 MPa, and a tensile modulus above 2 GPa [27,28]. Addi-
tionally, higher-surface-area biochar can enhance mechanical interlocking and increase the
mechanical stiffness of polymer composites [29].
Polymers 2023, 15, 3981 3 of 32

Figure 1. Structure and composition of lignocellulosic biomass.

Figure 2. Statistics of materials used in polymer matrix composites globally [24,25].

Polymers 2023, 15, 3981 4 of 32

3. Production of Polymer Composites through Extrusion and Casting

Polymer extrusion is a widely used high-volume manufacturing process in which
polymer resin, biochar filler, a compatibilizer, and other desired additives are melted and
formed continuously. The resulting material is then granulated, fed to a hopper, and
processed through a rotating screw in a feed throat [12,14,15]. In contrast, polymer casting
involves pouring a liquid polymeric material into a mold with a hollow cavity of the
desired shape and size and allowing it to cool to form a solid polymer [12–15,30]. The
polymer extrusion process consists of five stages, beginning with the addition of raw
plastic materials like granules and pellets to a hopper, which is then fed into a long heated
cylindrical extruder using a rotating screw. The raw material flows down the hopper
through the feed throat and large spinning screw within a horizontal barrel. The heating
temperature for processing the raw materials is set depending on the type of polymer. The
extruded polymer is fed onto a conveyor belt for cooling by air or water medium [31–35].
The polymer die is designed to ensure that the polymer flows smoothly from the extruder
and is shaped.
In the polymer casting process, a mandrel or inner diameter mold is immersed in
a polymer solution or molten plastic, forming a thin film around the mold. The mold is
then extracted in a controlled manner, followed by a curing or drying process [36–42]. In
polymer extrusion, extensional flow orientates the polymer molecules more effectively
than in casting. The extruded polymer tends to have fewer inclusions and defects than
casted polymer composites due to higher concentration of solid particles in polymer
composites [43–47]. The casting process involves introducing liquefied plastic onto a
mold and allowing it to cool down and solidify at atmospheric pressure [36,48]. However,
polymers with inconsistent viscosity at elevated temperatures, such as polyoxymethylene
(POM), polycarbonates (PCs), and polypropylene (PP) are not suitable for the casting
process. During casting, the transition from liquid to solid is achieved either by evaporation,
chemical action, cooling, or an external heating source [36]. Both described methods are
widely used in production of biochar-reinforced composites and nanocomposites. Figure 3
describes the schematic of two main methods in fabrication of nanocomposites in academic
and industrial settings.

Figure 3. Schematics: (a) single-screw extruder with its different parts showing the simplified process
of extrusion; (b) polymer solution casting method in fabrication of composite materials.
Polymers 2023, 15, 3981 5 of 32

4. Types of Carbon-Based Filler Materials and Their Properties

Utilization of carbon-based composite fillers depends on various factors such as man-
ufacturing cost, tensile strength, and mechanical and electrical properties. Some widely
known composites include carbon filaments, carbon nanotubes, and carbon black [7,8].
The addition of carbonaceous fillers enhances heat resistance, stiffness, and creep reduc-
tion; reduces flammability; increases compressive strength; improves abrasion resistance;
decreases permeability; and improves tensile, impact, and flex strength. It also improves
the thermal conductivity, processability, moisture resistance, and adhesion properties of
polymer composites.

4.1. Carbon Black

Carbon black is an inorganic material produced by the reaction of hydrocarbon fuels
in a limited oxygen supply at elevated temperatures above 1300 ◦ C. Carbon black is a
colorant and reinforcing filler used in various products, such as rubber, polymers, and tires,
and improves mechanical properties, affects compound properties, such as viscosity, and
has a strengthening effect on compounds [7,49]. Carbon black has an amorphous structure
and is synthesized through incomplete combustion of coal, tar, or petroleum products,
including fuel oil, in the absence of oxygen [50]. Carbon black exists in three forms: thermal
black, channel black, and lamp black following different ASTM standards including N220
and N326. Carbon black has the advantage of tunable electrical conductivity in polymer
composites. The high environmental impact of the production of carbon black relies on
the oil industry as well as environmental and health concerns which is a major drawback
for its usage in polymer composites [51]. Carbon black is supplied in various solid forms
including powder form and has high melting and boiling point and is derived from
petroleum products. It has a specific gravity between 1.8 and 2.2 and is highly combustible
with oxidizers. It is a highly sought-after material, whose demand exceeds 8 million tons per
annum, primarily used in polymer composites to increase modulus and tensile strength. It
is crucial to add an appropriate concentration of carbon black to achieve optimal strength in
these composites, as high concentrations may reduce tensile strength at high loadings. The
addition of carbon black at the right loading levels is necessary to enhance the mechanical
and electrical properties of rubber and polymer composites. It contributes to increase the
glass temperature (Tg ) of polymer composites as well as the microhardness [49,51]. The
reinforcement effects are controlled through the molecular interaction between polymer
molecular structure and carbon black. Experimental investigations found that carbon black
increases tensile ductility by a factor of 3 achieving up to 100 MPa in polymer composites,
with 7 wt.% filler weight percentage [50]. The addition of carbon black improves the tensile
and flexural strength, Young’s modulus, and crystallization behavior of polymer composites
by offering more nucleation crystallization sites [52,53]. X-ray diffraction analysis (XRD)
identifies the improvements of crystalline behavior using fillers and has shown that carbon
black improves the mechanical properties of polymers such as vinyl ester by the addition
of carbon black by 5 wt.% [49,51]. Carbon black also prevents ultraviolet degradation and
improves plastic conductivity and overall mechanical performance by enhancing abrasion
resistance, modulus, tear, and tensile strength [50,54]. Carbon black dispersion and wt.%
loading have an impact on the mechanical properties of composite materials which varies
between 5 wt.% and 30 wt.% [50,54]. Experimental investigations found that the addition
of carbon black by 4 wt.% to ester-based polymer compounds increased tensile strength by
30%, flexural strength by more than 40%, and flexural modulus by over 65%. The optimum
Young’s modulus achieved in polymer composites using carbon black was reported at
4 wt.% [51]. Also, the highest improvements in mechanical properties are reported by the
addition of polymer composites with less than 10 wt.% carbon black as a filler [54]. The
electrical conductivity of carbon black exceeds that of carbon nanotubes at the same volume
due to the dispersion limitations and low conduction threshold compared to carbon black
polymer composites [55]. The molecular structure and aggregated particle size of carbon
nanotubes are shown in Figure 4.
Polymers 2023, 15, 3981 6 of 32

Figure 4. Aggregated particle size of carbon black.

4.2. Carbon Nanotubes

Carbon nanotubes are produced from processes such as arc discharge, chemical vapor
deposition, and laser synthesis. They are considered a highly effective filler which can
potentially improve the performance of polymer composites, enhance the electrical and
thermal conductivities, increase mechanical strength, and possess a high length-to-diameter
ratio (1000:1). The expected filler concentrations of carbon nanotubes are between 0.5 wt.%
and 30 wt.% based on the mechanical structure of the polymer composite [56]. Carbon
nanotubes enhanced the mechanical properties and improved Young’s modulus of polymer
composites to above 3000 MPa, achieving tensile strength above 30 MPa, and fracture
strength that exceeds 100 MPa with more than 3 wt.% filler loading. In rubber composites,
modulus and tensile strength have shown improvement by 28% and 25%, respectively, by
the addition of 0.1 MWCNT parts per hundred of rubber (phr) [57]. The addition of 3 wt.%
MWCNTs increased the toughness and retained the stiffness of polymer composites [58].
CNTs with lower loading (1.75 wt.% by weight) have shown improvement in fracture
strength and an increase in thermal conductivity resulting in a reduced number of adiabatic
shear bands and a reduction in thermal softening at high cutting velocities. CNTs with high
loads above 5 wt.% by weight, affect the mechanical properties and machining response
in polymer composites. Also, the addition of carbon nanotubes to ABS composites has
increased the flexural module by 17–30% [54]. The high production cost of carbon nanotubes
makes them unsustainable fillers in polymer composites. At different CNT loads below
1 wt.%, a 22% improvement in tensile strength is observed in polymer composites while
a high flexural strength reaching 400 MPa is achieved by only 0.25 wt.% [59]. Polymer
composites with only 1 wt.% CNT have shown improvement in damping properties and
better molecular interaction between fiber and polymer composites [60]. The application of
carbon nanotubes as a reinforcing filler in polymers enhances electromagnetic interference
(EMI) shielding due to its large surface area, 3D networking structure, and unique electronic
structure [50,61]. The trends obtained for nanocomposite mechanical properties indicate
improvement in storage and loss modulus by increasing CNT loading from 0.5 wt.% to
4 wt.% [62]. The polymer composites containing 4 wt.% MWCNTs have shown similar
tensile strength to those with 20 wt.% woody biochar [63]. Mechanical tests on CNTs have
shown high elasticity modulus above 1 TPa. Carbon nanotubes have 10–100 times greater
Polymers 2023, 15, 3981 7 of 32

mechanical strength when compared to steel at a fraction of the weight. Additionally,

CNTs have excellent thermal stability and could withstand up to 2700 ◦ C and electrical
conductivity up to 100 S/cm [63,64]. Single-walled CNTs have a hexagonal honeycomb
structure of sp2 which MWCNTs have multiple concentric tubes circling one another [62]. A
major advantage of CNTs in terms of electrical properties is that 4 wt.% loading of MWCNTs
indicated the same effect in terms of electrical conductivity as that for 20 wt.% biochar
filler in polymer composites. The mechanical structure of carbon nanotubes is shown
below in Figure 1. A major disadvantage of carbon nanotubes is their lack of solubility
in aqueous media, which hinders their use as a filler material in polymer composites [13].
The molecular structures and aggregated particle sizes of carbon nanotubes are shown in
Figure 5.

Figure 5. Chemical structure and morphology of carbon nanotubes. (a) Cross-sectional view, and
(b) side view of its structure and atomic arrangement.

4.3. Carbon Filaments and Fibers

Carbon filaments are composite materials formed by infusing carbon fragment fibers in
polymer structures. Examples of widely used filament materials in engineered thermoplas-
tics are polylactic acid (PLA), synthesized nylon polymers, or polyethylene tetra-phthalate
glycol (PETG) [12,65]. These are also known as carbon-fiber-reinforced polymers (CFRP),
made from a matrix and a reinforcement material. In carbon-fiber-reinforced polymers,
carbon filaments improve mechanical strength while polymer resins such as binds improve
the polymer matrix and molecular interaction between fillers and polymer composites.
It is estimated that carbon fiber is five times more effective as a reinforcement material
than steel and has a higher stiffness than steel. In addition, the low weight of carbon fiber
makes it an ideal reinforcement material in polymer composites. Carbon fibers synthesized
from pyrolysis are added to composites and polymer matrix materials as fillers. Carbon
filaments are synthesized using high-temperature catalytic reactions from carbon-based
gases at temperatures between 450 and 700 ◦ C [66–68]. Carbon fibers are synthesized at
operating temperatures above 200 ◦ C by passing oxidized fibers prepared using oxygen
and to pass the oxidized fibers at inert conditions and operating temperatures between
400 ◦ C and 1500 ◦ C for fiber carbonization [66]. Integration of carbon fibers into polymer
composites such as acrylonitrile butadiene styrene (ABS) increased tensile strength by
39%, reaching 37 MPa, and increased Young’s modulus by 60%, reaching 0.79 GPa [69].
Conventional carbon fibers and filaments produced from biomass pyrolysis differ in the
carbon microstructure. To produce highly effective fibers with a high degree of orientation,
precursor fibers are given mechanical stretching treatment during the pyrolysis process [70].
Carbon filaments are synthesized by a top–down approach using thermal treatment tech-
niques formed by infusing fragments of carbon fibers in polymers. Carbon filaments are
Polymers 2023, 15, 3981 8 of 32

produced in a rotating quartz tube furnace under inert conditions at operating tempera-
tures between 400 ◦ C and 1600 ◦ C. The precursor fiber could be either polyacrylonitrile or
pitch fiber precursor through heated oxygen where oxygen is absorbed and then passes
through the carbonization process. Carbon filaments are then synthesized by infusing
fragments of carbon fibers at operating temperatures between 250 ◦ C and 700 ◦ C in a batch
process [69–71]. High carbide content is required as a prerequisite for the nucleation of
carbon filaments. Table 1 presents a summary of the mechanical properties, including
elastic modulus, tensile modulus, and ultimate strain, of different carbon-based fibers.

Table 1. Typical mechanical properties of different types of carbon fibers.

Elasticity Tensile Strength Ultimate Strain

Carbon Fiber Fiber Mechanical Strength References
Modulus (GPa) (MPa) (%)
Pan-based fiber High modulus 300 5000 1.73
Hysol Grafil Apollo Ultra-high modulus material 450 3500 0.77
[67,72]
Pitch-based fiber High-quality fiber 227 2758 1.76
Hysol Union Carbide High modulus 240 3440 1.75

Carbon fiber layers consist of carbon filaments that have carbon layers whereas the
filament arrangement is affected by the synthesis process conditions during the filament
fabrication [28]. At the same volume fraction, carbon filaments have lower tensile strength
and stress compared to carbon fibers with the same volume in a reinforced polymer
composite [68]. For instance, carbon filaments at a filler loading of 18 vol.% have 20 times
higher tensile strength compared to the same volume fraction of carbon fibers yielding
a tensile strength of more than 20 MPa [67,68]. Table 2 presents a comparison between
biochar, carbon nanotubes, and carbon filaments as fillers.

Table 2. Comparison of composites reinforced with biochar, CNT, and carbon filaments.

Filler Material Biochar CNT Carbon Filaments References

Carbon fibers are
Produced by either catalytic converted to long strands
Raw material and its Synthesized by pyrolysis
chemical disposition, laser and heated to very high
production method above 500 ◦ C.
ablation, or arc discharge. temperatures without
contact with oxygen.
Improves thermal stability.
Addition of biochar Film and rigid mechanical
CNT possess excellent
between 20 wt.% and structure; high tensile
Advantage of filler adsorption ability due to
30 wt.% increases the glass strength and stiffness; [11,43,67,68,73]
material strong interaction with heavy
transition temperature of high chemical and heat
metal ions.
the polymer composite by resistance.
7–20 wt.%.
Homogenous dispersion of
The properties of biochar
CNTs is difficult especially at
depend upon properties of
high loadings.
biomass and thermal High production cost;
Disadvantage of filler Molecular modification is
conditions during negative temperature
material needed to enhance dispersion
pyrolysis. Different coefficient of resistance.
and reduce aggregation. Also,
biochar yields different
they have a very high cost
mechanical properties.
compared to alternative fillers.

4.4. Graphite and Graphene-Related Materials

Graphene, a single layer of graphite, possesses distinctive characteristics such as
remarkable conductivity, strength, and thermal stability. These exceptional properties
make it possible to integrate this material into polymer composites as nanofillers, thereby
improving their overall properties. The trend in recent years has seen a shift towards
slimmer and more compact designs for electrical devices. Consequently, effective heat
management has emerged as a crucial consideration in both device and application design.
Polymers 2023, 15, 3981 9 of 32

This challenge extends to various other applications like electric motors, generators, power
generation heat exchangers, and automotive systems, all of which grapple with similar
thermal issues. The incorporation of thermally conductive fillers into polymer-based
composites has significantly enhanced their thermal conductivity performance. As evident
from the aforementioned points, graphite is gaining increasing popularity for its ability
to improve the thermal conductivity of composites across a wide range of applications.
The nanostructure of graphene allows it to be an effective sustainable filler for different
kinds of thermoplastic polymers or thermosetting resins with unique mechanical and
chemical properties.
In the presented study, the solution-casting method was employed to fabricate PSU-
based composites filled with various filler concentrations, reaching up to 70 wt.%. Three
different types of graphite were utilized as fillers to enhance both thermal conductivity and
mechanical properties. Upon investigating the morphology and structure of these fillers,
it was observed that natural graphite possessed a flawless crystalline graphite structure,
making it the most effective filler in enhancing the composite’s thermal conductivity [74].
Regarding the thermal conductivity of the composite, the highest value was achieved
using 70 wt.% natural graphite, reaching approximately 4.26 W m−1 K−1 . This superior
performance can be attributed to natural graphite’s perfect crystalline structure and its
large aspect ratio, which results in a substantial conducting surface area interacting effec-
tively with the matrix, facilitating more efficient heat transfer compared to other types of
graphite [75].

4.5. Biochar
Biochar is a carbon-rich material, which is abundant and prepared easily from various
types of biomasses. Biochar has superior characteristics including hydrophobicity, high
surface area, and porosity, which improves its mechanical and thermal properties [2,23].
Addition of biochar improves the thermal stability of polymer composites due to the
nitrogen- and oxygen-containing functional groups existing on the surface of biochar [4,69].
It also improves the physical adsorption capacity of polymer composites through enhanced
molecular interactions such as hydrogen bonding [2,22,76]. Additionally, the thermal
stability of biochar can be adjusted between 0.10 and 0.13 W m−1 K−1 depending on
the different pyrolysis temperature profiles which produce differences in microstructure,
minerology, and physicochemical properties [4,22,76,77].
The incorporation of biochar- or wood-based materials into the matrix increases the
polymer hardness by achieving mechanical interlocking of the polymers with biochar;
this is possible because of the enhanced matrix wettability granted by the large surface
area of biochar. The bulk properties of polymer composites are predicted using various
theoretical models such as the Halpin–Tsai–Nielsen and Verbeek models. Addition of
biochar increased different polymer composite hardness.
By increasing the operating temperature from 600 ◦ C to 800 ◦ C, the porosity and
surface area increase, forming graphite-like molecular domains which contribute to increase
in the mechanical hardness. Higher operating temperatures lead to progressive enlargement
and ordering processes of graphic domains through turbostratic rearrangement [2,69,70].
The properties of biochar, such as surface area, porosity, and grindability, are controlled
by several factors, such as d morphology, chemical composition of feedstock, and the type
of post-treatment technique used, e.g., physical activation or surface tailoring [70,71,78].
The thermochemical processes chosen for production of biochar play a critical role in
determining the final physical properties of the biochar filler. The different parameters
such as production temperature, reactor dimensions, and lignin content in feedstock play a
role in controlling the porosity and surface area of biochar [70,78].
A decrease in the pyrolysis operating temperature to 450 ◦ C causes a decrease in the
functional groups and reduces the affinity of biochar towards polar moieties [79,80]. Biochar
produced at high temperatures above 700 ◦ C has decreased O/C and N/C ratios due to
temperature-induced dehydration and the carboxylation process [4,81,82]. Additionally,
Polymers 2023, 15, 3981 10 of 32

the solvent absorption capability of the biochar improves due to the formation of more
non-porous structures. The development of fire resistance in biochar is a result of the
formation of compact carbonaceous layers which prevent the transfer of oxygen towards
the polymer matrix [4,81].
The mechanical characterization of biochar polypropylene composites show that the
addition of between 20 and 24 wt.% of biochar produces similar tensile strength but higher
modulus strength and flexural properties [4,81]. However, the addition of biochar beyond
15 wt.% in polymer composites reduces the material ductility. In terms of fire-resistant
properties, biochar samples produced from pyrolysis at 500 ◦ C and activated at 900 ◦ C
have shown exceptional fire-retardant properties [83].
The type of biomass feedstock influences the main mechanical characteristics of biochar
such as pore volume and ash content. Biochar with higher carbon content and higher sur-
face area exhibited higher tensile strength and modulus [83]. Biochar with high CaCO3
loadings have shown enhanced fire-resistant properties due to the inorganic content hinder-
ing the diffusion path of oxygen in polymer composites [4,82,84]. Furthermore, increasing
biochar content decreases the heat release rate and smoke production rate [4,77]. Introduc-
tion of higher biochar loadings also causes a monotonic increase in the tensile and flexural
moduli due to peculiar morphology of polymer composites [2,22,77].
The morphological properties of biochar as well as mechanical interlocks make it
an excellent filler in various polymer composites. The enhanced matrix wettability of
biochar caused by high surface area improves the mechanical interlocking properties of
polymer composites [4,77,85]. The moisture-holding capacity of biochar can be altered by
changing the operating temperature of pyrolysis or carbonization, which further improves
the moisture-holding capacity in polymer composites [4,22,77]. The existence of turbostrat-
ically ordered regions, arranged crystalline regions, and disordered amorphous regions in
cellulose enhance the electrical conductivity of biochar [2,22,70,78]. The honeycomb-like
pores on the biochar surface results in the improved mechanical interlocking of the poly-
mer with biochar causing it to be an excellent reinforcing agent [70,78,86,87]. The highest
improvement in tensile strength in polymer composites was observed by the addition
of 15 wt.% biochar resulting in a higher stress yield. Polymer composites with higher
biochar-loading rates (25, 30, and 35 wt.%) have shown semi-brittle behavior under tensile
strength [17,22,70,77]. The addition of biochar also increases the tensile modulus. Biochar
loading at 35 wt.% has shown a tensile modulus of higher than 3080 GPa [4,77,85]. Biochar
produced by carbonization or pyrolysis at high operating temperatures of 900 ◦ C enables
better stress transfer between polymer composite and biochar [4,22,77,85]. The addition
of biochar also increases stiffness, resulting in a lower percentage elongation for polymer
composites, with the best elongation reported at 15 wt.% biochar concentrations [88]. Both
the flexural strength and modulus have shown improvement with addition of biochar at
high loadings [2,69,70].
Also, the stress transfer caused by the addition of biochar in polymer composites
improves the mechanical properties between the filler and the matrix by obstructing
mechanical failure. The addition of biochar improves the cross-linking of the epoxy matrix
by blocking the movement of molecules, which in turn increases the strength of the polymer
composite [22,78,79,89]. The addition of biochar also enhances thermal conductivity values
and improves the tolerance of strain before reaching the glass transition temperature
(Tg ) [71,78,86,87]. The ultimate strength of around 40 MPa for polymer composites is
achieved by lower biochar filler loading; the strength decreases with an increase in the
biochar-loading rate. Deterioration in the load bearing capacity of polymer composites have
been shown to be a result of the transition of the polymer composite behavior matrix from
plastic to semi-brittle at high biochar load-bearing capacities [21,78,86]. The impact strength
for polymer composites is improved by the micro-hardness features of biochar [79,89].
Biochar filler particles with softer phase of hardening agent increase the degree of stress
transfer to filler particles [78,86]. The temperature of biochar carbonization affects the
mechanical properties and the tensile modulus of polymer composites.
Polymers 2023, 15, 3981 11 of 32

5. Use of Filler Materials in Polymer Composites: Effects and Limitations

Many polymer composites are prone to decomposition at high temperatures, which
can limit their applications in certain industries and environments. Moreover, polymer
composites, especially those reinforced with fibers, can be highly sensitive to moisture
absorption. The other limitations of polymer composites include poor toughness, bending
strength, and creep performance, which is defined as the tendency of the material to de-
form permanently under influence of mechanical stress [60,66,90]. The polymers owing to
these characteristics can undergo dimensional changes via either thermal or mechanical
degradation and hence decrease the strength and stiffness properties. Additionally, the
high fabrication cost of polymer composites at low production rates limits the widespread
adoption of polymer composites in various industries; therefore, new manufacturing tech-
nologies are required to reduce fabrication costs and make polymer composites more
economically viable [63,68]. Emerging technologies such as the incorporation of organic
sustainable fillers, e.g., biochar, aim to enhance the physical performances of polymers by
increasing their tensile strength and melting temperatures. However, the tensile strength
of the polymer matrix can be improved by the addition of compatibilizers, which are the
coupling agents added to immiscible materials during the extrusion process. This alters
the interfacial properties, stabilizes the melt blend [78,91], and enhances the mechanical
bonding strength and cross-linking of immiscible materials, such as biochar and polymer
materials, as well as enhancing the interfacial adhesion between polymer composites and
compatibilizers [90]. Non-reactive compatibilizers, including ethylene–ethyl acrylate (EEA),
are used as polypropylene polymers. Other compatibilizers, such as ethylene–butyl acrylate
and ethylene methacrylate (EMA) copolymer, used for the compatibilization of polypropy-
lene, polyethylene, polyethylene terephthalate, and acrylonitrile butadiene styrene, are
most widely used in polymer composites. However, frequently used reactive compatibiliz-
ers include acrylic-based/grafted polyolefin polymers, polyethylene, polypropylene, and
polybutylene terephthalate. The addition of compatibilizers to various polystyrene and
polypropylene compounds improves their mechanical properties, increases their tensile
strength by 20%, and increases their impact strength by 100% [60].
Various carbon-based fillers, including carbon black, are the oldest carbon fillers em-
ployed in the plastic and rubber industries. However, carbon fiber and graphite are more
versatile carbon alternatives because of their low cost and their capacity for mass produc-
tion, placing them at an advantage among other carbon-based polymer composites [92].
The enhancement of the physical properties of polymer composites by the addition of fillers
depends upon several structural parameters: homogeneous composition, morphology, size,
and aspect ratio of the fillers; the surface characteristics; the surface area; the interfacial
filler–filler interactions; and polymeric material and filler, etc. Additionally, the process-
ing and operating conditions, such as the mixing technique, loading rate, shear effects,
temperature, etc., have an observed effect [92]. Several researchers have focused on the
mechanical, thermal, and electrical characteristics of carbon-added polymeric composites
to investigate their potential applications in advanced technologies, including batteries,
sensors, solar cells, bipolar plates, and thin film applications [73,93,94]. For instance, the
addition of biochar has shown to bring about an increase in the oxidative stability and ther-
mal decomposition temperature (by 15 ◦ C) of polymer composites [29,90]. However, the
addition of organic fillers to polymeric materials leads to distinct characteristics compared
to control polymeric materials; this requires further investigation to be better understood.

5.1. Effects of Filler Addition on the Mechanical Performance of Polymer Composites

There are several mechanical limitations of polymer composites that could be im-
proved by biochar organic fillers such as lower fracture toughness, flexural strength flexural
modulus, and hardness [73,78,91]. As the volume of filler increases, the modulus of rupture
and the flexural modulus, as well as material toughness, increase. The most recommended
filler volume for mechanical toughness is approximately 55% by volume [90,94]. The shape
of biochar filler particles influences filler volume. For example, irregular biochar fillers have
Polymers 2023, 15, 3981 12 of 32

low filler volume (between 25 wt.% and 51 wt.%), whereas biochar in round particles has
high filler content up to 60 wt.%. Polymer composites with high filler content exhibit high
flexural strength up to 120 MPa, flexural modulus (12–15 MPa), and the highest toughness
achieved at filler volume 55 wt.% [94].

5.2. Thermal Conductivity in Polymer Composites

Thermally conductive polymer composites are considered to be promising materials
due to their multiple applications in electronic equipment [95]. Biochar fillers in polymer
composites achieve good tensile and flexural properties and improve the thermal stability
and ductility of polypropylene-reinforced composites [96]. The addition of biochar en-
hances thermal properties due to the high surface area and microhardness of biochar that
achieves mechanical and thermal improvements in various polymer composites. One of
the current limitations of reinforced polymer composites is their low electrical conductivity
compared to metallic-based fillers, which limits their industrial applications [97]. The
composition of the feedstock also affects the expected cost and CO2 emissions from slow
pyrolysis. Cellulose, hemicellulose, and lignin are the main components of most biomass
feedstocks, and they have different properties and behaviors during pyrolysis. For example,
cellulose is the most reactive component and tends to produce more gases and char, while
lignin is more stable and tends to produce more solid and liquid products. In general,
lignocellulosic biomaterials (such as wood and agricultural residues) represent a more
cost-effective type of feedstock for slow pyrolysis in the production of char, which can be
used as a filler material in polymer composites. Figure 6 presents the expected biochar
product yields and CO2 emission rates from different types of feedstocks.

Figure 6. Slow pyrolysis: expected costs and CO2 emissions from different components of feedstocks
from slow pyrolysis [15]. This provides examples of various interactions on the surface of biochar
particles and biochar–matrix interactions.

6. Biochar Properties and Biochar’s Impact as a Filler in Polymer Composites

Slow pyrolysis at lower heating rates (<10 ◦ C min−1 ) produces a high biochar product
yield and is recommended due to the high conversion rate and ease of operations, economic
feasibility, and maintenance [98,99]. Biochar physicochemical properties are regulated by
feedstock properties and pyrolysis conditions, such as temperature profile, reaction time,
reactor configuration, and temperature profile [98,100,101]. During carbonization, heating
rate and heat dissipation affect the physicochemical properties of biochar which influences
Polymers 2023, 15, 3981 13 of 32

the energy content, product yield, carbon content, porous structure, and biochar pH value.
At high operating temperatures, the pore size and volume increase, and the increase in the
biochar surface area is caused by the change of carbon phase from an amorphous structure
to graphite. For example, the biochar surface area at 400 ◦ C from sawdust has a surface
area of 147 m2 g−1 and increases to 570 m2 g−1 by increasing the operating temperature
to 700 ◦ C [2,4,70,89]. It is necessary to develop methods which can produce high biochar
porosity and longer pyrolysis residence time that exceeds 60 min [102]. Physical activation
methods are carried out using carbon dioxide or steam, while chemical treatment activation
is carried out by acid, alkaline, and oxidizing or reducing agents to increase biochar surface
functionality. Biochar properties, including surface area, pore size, and pore structure,
increase adsorption capacity and carbon dioxide storage capacity; this improves both
surface functionalities and mechanical properties [103,104]. Biochar’s inherited properties
are greatly dependent on its physical structure and operating conditions during biomass
pyrolysis. Properties such as electrical conductivity are also controlled by the internal struc-
ture of biochar [2,4]. Slow pyrolysis is the most frequently recommended thermochemical
reaction for producing a large yield of biochar. Depending on the biomass feedstock used,
e.g., wood, straw, green waste, or dry algae, biochar yields vary from 20 wt.% to 90 wt.%,
depending on operating conditions [70,98,105]. It is noted that, at higher pyrolysis operat-
ing temperatures, the highest biochar yields are achieved. For example, for slow pyrolysis
using wood biomass, at 300 ◦ C and 10 min residence time, biochar yield is 89 wt.%, while
at 600 ◦ C and 10 min residence time, biochar yield is higher [68,105,106]. Table 3 presents
a summary of biochar and hydrocarbon product yields obtained from different pyrolysis
and carbonization operating conditions [1,9,107].

Table 3. Expected biochar and hydrocarbon product yields from biomass pyrolysis at different
heating rates.

Vapor Residence Heating Rate Process Solid Yield Liquid Yield Gaseous
Pyrolysis References
Time (s) (◦ C) Temperature (◦ C) (wt.%) (wt.%) Yield (wt.%)
Slow 450–500 0.1–1 300–700 ~35 ~30 ~35 [21,89,108]
Fast 1–10 10–200 400–800 ~20 ~50 ~30 [45,46,108]
Flash <1 ~1000 800–1000 ~12 ~12 ~75 [20,21,108]

Rotary kiln reactors are recommended for slow pyrolysis and high-temperature reac-
tions with long residence time at slower heating rates for increasing biochar product yield.
However, this type of reactor is not recommended for high-level production of bio-oil. More
specialized reactors have been developed that produce higher biochar yields [70,98,105].
The most important operational factors in chemical reactors are the operating temperature,
the heating rate, the separation and cooling of vapors, and the gas cooling system. In
fixed-bed reactors, solid residue and biochar are collected at the bottom of the reactor and
contacted by either a counter or a co-current gas stream. Biochar is collected from the bot-
tom of the chemical reactor. Fixed-bed reactors are mostly recommended for slow pyrolysis
and carbonization processes which have longer residence time. Fixed-bed reactors could be
used in biomass carbonization, pyrolysis, or gasification [100]. Fluidized-bed reactors are
mostly recommended for biomass gasification reactions. Fluidized-bed reactors are recom-
mended for higher heat and mass transfer between solid and gas particles. Fluidized-bed
reactors are efficient reactors for rapid heat transfer with different configurations including
vertically upward and vertically downstream. Fluidized-bed reactors are either heated by
direct heat or indirect heat transfer. Another advantage of fluidized-bed reactors is their
ability to operate at lower operating temperatures for a long residence time. The optimal
biochar yields produced from biomass in fluidized-bed reactors are between 25 wt.% and
45 wt.%; these are affected by the heating rate and the temperature profile used, depending
on the operating conditions and lignin content in biomass feedstock [2,71,89]. Ablative
reactors are recommended for fast pyrolysis for processing various types of lignocellulosic
Polymers 2023, 15, 3981 14 of 32

feedstock with high energy density requirements. Ablative reactors are mostly recom-
mended for more intense reactions without the need for inert gas to operate. Ablative
reactors are recommended for intense reactions with high heat transfer. An advantage
of ablative reactors includes a high recovery rate of liquid and gaseous products under
high pressure caused by mechanical centrifugal force. Pyrolysis reactions are carried out
in ablative reactors between 500 ◦ C and 600 ◦ C [3,70,78]. Augur reactors have a similar
product yield for hydrocarbon liquid products and char, like those from fluidized-bed reac-
tors. Augur reactors have higher heat transfer efficiency and yield high char production
from slow pyrolysis. For fast pyrolysis, liquid hydrocarbon product yields are maximized.
Biomass is rapidly converted to bio-oil, biogas, and biochar. Biochar drops to the bottom
of the reactor and hydrocarbon gases and liquids collect into the cyclone. Spouted-bed
reactors are recommended for biomass flash pyrolysis that allows continuous feeding and
versatility in gas flow; this makes this reactor suitable for handling solid particles, such as
biochar. It produces high yields of biochar compared to other reactor configurations.
Different kinds of composite materials are based on the polymer matrix and can de-
velop high-performance polymers with better mechanical, thermal, and chemical resistance
that can withstand harsh environments and applications with a reduction in production
costs [64]. Carbon-based materials, such as carbon black, carbon nanotubes, graphene, and
carbon filaments are introduced into polymer composites due to ease of use, large surface
area, and high thermal, chemical, and mechanical stability, and can be used as nanofillers
to enhance the performance of polymeric membranes [13,59]. Biochar is considered a cheap
biomaterial, and its physical properties could be controlled via operating conditions of
pyrolysis or carbonization. Biochar’s high surface area and high mechanical performance
have shown up to 35% improvement in flexural strength compared to other filler materi-
als such as conventional glass-fiber-reinforced polymers (GFRPs) [29]. Additionally, the
addition of biochar to polymer composites could reduce their material density. At higher
temperatures of pyrolysis, biochar’s pore volume and surface area increase due to lower
biochar particle density [109–111]. The tensile performance of polymer composites is tested
according to ASTM-D 638 standards. The addition of 4 wt.% MWCNTs achieves a 13%
higher Young’s modulus, while the addition of 20 wt.% as an organic filler increases the
Young’s modulus of polymer composites by 60% [63]. Therefore, biochar is considered to
be a better and cheaper filler in polymer composites related to CNTs. Also, the integration
of biochar in polymer composites increases the hot–wet use temperature and fracture
toughness of materials that could be used in aerospace applications. Biomass feedstock also
has an impact on the quality of biochar and filler properties in polymer composites. Factors
that affect biochar’s properties are the pyrolysis operating temperature, the reactor design,
and the feedstock; these control the physical performance of biochar, e.g., the particle size
and porosity [112].
Biochar with high porosity achieves higher thermal stability in polymer composites.
Biochar is compared to various organic and inorganic fillers. This section summarizes
the effects of biochar properties and pyrolysis conditions on polymer properties in terms
of crystallinity, thermal stability, flammability, electrical conductivity, and improvement
in mechanical and electrical properties. Biochar has an impact on the crystallization
temperature (Tc ) and thermal performance of polymer composites [105]. The higher surface
area in biochar, lower bulk density, high cation exchange capacity (CEC), and high carbon
content have a positive impact on the mechanical and electrical performance of biochar
in polymer composites [4,106]. The degree of crystallization is measured using an X-ray
diffractometer to analyze the crystalline structure of the reinforced polymer composite.
Biochar polymer aspect ratio, biochar filler loading, and nucleation have an impact on
the crystallization properties of polymer composites. The biochar surface area and microp-
orous structure is controlled by pyrolysis operating conditions and act as a nucleation agent
for crystallization. The addition of biochar particles into a polymer composite structure
improves the overall thermal performance and shifts the crystallization temperature (Tc) ten
times higher in polymer composites [105]. A thermogram of polypropylene-reinforced poly-
Polymers 2023, 15, 3981 15 of 32

mers shows that biochar raises their crystallization temperature and melting enthalpy. The
degree of crystallinity (Xc ) after biochar enforcement in polymer composites is calculated
using Equation (1):
∆Hm
Xc (%) = (1)
(1 − ∅)∆Hm ◦
where Xc is the crystallinity in biochar, ∅ is the biochar weight fraction in the polymer
composite, and ∆Hm ◦ is the enthalpy of melting a 100% crystalline neat polymer composite.
The thermogravimetric analysis can be used to measure the thermal stability of biochar
in polymer composites, while polarized light microscopy can be used to investigate the
impact of the addition of biochar on the morphological behavior of biochar in polymer
composites [105].
The thermogravimetric analyzer calculates the thermal stability of biochar in polymer
composites, while polarized light microscopy is used to observe the effect of biochar
incorporation on the morphology of biochar and polymer composites. Results have shown
that the incorporation of biochar in polymer composites increases the thermal stability and
thermal resistance of polymer composites; allowing them to tolerate temperatures 80 ◦ C
higher than those tolerated by neat polymer samples [105]. Biochar has shown similar
electrical performance compared to graphene and carbon black with better environmental
aspects such as recyclability and sustainability. More experimental analysis is needed to
determine the optimal biochar loads and the effects of the physical properties of biochar
to optimize the mechanical and electrical performance of polymer composites using cost-
effective manufacturing techniques.

6.1. Effects of Biochar Addition on the Thermal Stability of Polymer Composites

Enforcement of biochar as a filler has a positive impact on the thermal properties of
polymer composites and improves the thermal performance, as well as increasing the melting
point and the flammability limit of polymer composites. Polymer composites with biochar
fillers have shown higher thermal stability than neat polymers. For example, the addition
of 15 wt.% biochar to polypropylene increases the degradation temperature from 390 ◦ C to
412 ◦ C. Thermogravimetric analysis can be used to measure the thermal stability of polymer
composites with different biochar loads; for example, biochar at 20 wt.% loading was found
to increase the thermal stability of polypropylene to temperatures which were 80 ◦ C higher
than those tolerated by samples without biochar [105]. Biochar at certain loads causes a
significant decrease in thermal conductivity and diffusivity [77,84,86,112–114]. Experimental
results have shown that the addition of 5 wt.% of biochar increases the tensile modulus and
improves the mechanical strength of various polymer composites [115]. Hence, the usage of
optimized biochar loading improves the mechanical strength of plastic composites as well
as their thermal stability. Addition of higher loads of biochar decreases the hydrophobic
behavior of the polymer due to the hydrophilic characteristics of biochar [115]. Polymers
have poor mechanical properties; biochar fillers could enhance the mechanical, thermal,
and electrical properties of polymer composites. The high surface area of biochar improves
the mechanical interlocking and thermal stability of polymer composites, which can be
validated using thermogravimetry [78].

6.2. Effects of Biochar Addition on Flammability and Flame Retardancy

The thermal stability of polymer composites, such as polypropylene, has been shown
to be increased by biochar loadings of 15 wt.%, 25 wt.%, 30 wt.%, and 35 wt.%; these can
be processed using different mechanical processes, such as injection molding and extru-
sion [90]. Polymer composite mechanical testing is performed using cone calorimetrics,
thermogravimetric analyzers, X-ray diffraction, and IR spectroscopy [89]. Experimental in-
vestigations have found that biochar at 10 wt.% loading in polymer composites achieves the
highest flame-retardant properties and thermal stabilities [116]. The loads of biochar which
are most recommended for enhancing mechanical properties are those between 15 wt.%
and 30 wt.%; higher loadings of biochar deteriorate the mechanical properties [90,117,118].
Polymers 2023, 15, 3981 16 of 32

The addition of biochar reduces the peak heat-release rate and smoke-release properties
of polymers due to the flame-retardant properties of biochar. Biochar with higher surface
areas, produced at high operating temperatures, creates a mechanical engagement that im-
proves the mechanical properties of polymers [119]. High thermal stability, measured using
thermogravimetry, has been detected in polypropylene composites, and this is attributed to
the flame-retardant properties of biochar as a filler [119]. The addition of biochar has been
shown to improve heat resistance, increase resistance to flames, reduce smoke-production
rates [120].

6.3. Electrical Conductivity of Polymers by Addition of Conductive Fillers

All polymer composites have a degree of preferred physical orientation in terms of
resistivity measurement. For electrically conductive fillers, the mechanical behavior of
polymer composites decreases with increasing filler volume fractions [74]. At a constant
filler volume, as the carbon fiber length increases, the electrical conductivity decreases due
to higher resistivity. For example, at a constant filler volume of 40 wt.%, the resistivity
of 200 µm is 0.038 ohms, while the resistivity of 400 µm is 0.011 ohms [74]. The electrical
conductivity in polymer composites can be measured using several techniques, such as
voltmeters [117,118,121]. Figure 7 presents an example of the measured electrical conduc-
tivity in polyvinyl alcohol polymer composites at different biochar loads of 2 wt.%, 6 wt.%,
and 10 wt.%.

Figure 7. Electrical conductivity at different filler loadings of biochar in PVA polymer composites [22,23].

The usage of fiber-reinforced polymers with continuous filaments of highly electri-

cally conductive materials improves the electrical conductivity through the creation of
interconnected pathways that improve current flow [122]. Experimental investigations
have shown that the existence of orthogonally conductive z-filaments in carbon epoxy
composites creates conductive pathways; this can be used in the development of electrically
conductive biochar. There is a demand for the development of highly conductive carbon
filaments to improve electrical conductivity in various composite materials, as well as their
mechanical and thermal properties [123].

6.4. Impact of Biochar Filler Loading on Other Mechanical Properties

The replacement of carbon fibers with carbon filaments in composite materials has
shown improvement in electromechanical performance and noise control [67]. Experimental
investigations have shown that the usage of short carbon fibers favors high conductivity and
polymer properties are affected by filler content and glass temperature as well as the degree
Polymers 2023, 15, 3981 17 of 32

of filler dispersion. Also, investigations suggested that energy consumption increased with
higher dispersion of filler content [90]. Biochar extracted from poplar plants mixed with HDPE
improves the flexural strength of HDPE polymer composites. However, biochar loadings
higher than 70 wt.% lead to a reduced flexural strength compared to pristine HDPE [61,86,105].
Higher biochar content leads to a higher agglomeration degree that improves mechanical
properties, such as flexural strength, compared to neat polypropylene from 50 MPa to 59 MPa
with the addition of more than 30 wt.% biochar [78,90,105]. Polymer composites with high
flexural strength reaching 140 MPa had biochar loading at 55 wt.% [96].
Experimental investigations have shown that biochar obtained at lower pyrolysis tem-
peratures (300 ◦ C to 400 ◦ C) has the highest tensile strength, whereas biochar obtained with
pyrolysis temperatures between 600 ◦ C and 900 ◦ C has the same mechanical strength. Biochar
derived from bamboo plant shells has shown better mechanical properties than other types
of biochar such as coconut shells due to high fiber content [124]. Biochar produced from the
bamboo plant has shown better water resistance, thermal stability, and mechanical properties.
The optimal temperature for achieving hydrophobicity in polypropylene composite materials
is found at 300 ◦ C for biochar [124]. Also, the addition of biochar at different loads to thermo-
plastics such as polylactic acid (PLA) has different effects based on different biochar (BC) loads
ranging from 5 wt.% to 25 wt.% [86,98]. For example, biochar loading at 5 wt.% improves the
elasticity tensile modulus by 38% and decreases the tensile strength by 5% [115]. Increasing
the biochar content could lead to a reduction in the tensile modulus of elasticity [115]. For
example, as shown in Figure 8, the optimal loading of poplar biochar to HDPE composites at
46 wt.% achieves the highest flexural strength while any further addition of biochar weakens
the HDPE polymer flexural strength [82]. Table 4 summarizes the improvements in acoustic,
thermal–mechanical, and electrical properties of different polymers at various biochar loads.

Figure 8. Effects of the addition of different loads of biochar on the flexural strength of HDPE polymer
composites [83].

Table 4. Polymer composites prepared with different biochar sources, loads, and fabrication methods.

Carbonization
Polymer Biochar Source Filler Loading Rate Fabrication Method References
Temperature (◦ C)
High molecular Compression
Bamboo tree 5 to 9 wt.% 1000
polyethylene molding
Biochar synthesized
from wood (50 to [12,13]
100 µm) Extrusion and
Polyethylene 24 to 30 wt.% 900
(MAPP) injection molding
Biochar (1000 µm
and 50 µm)wood
Polymers 2023, 15, 3981 18 of 32

Table 4. Cont.

Carbonization
Polymer Biochar Source Filler Loading Rate Fabrication Method References
Temperature (◦ C)
Miscanthus grass
Polypropylene (106–125 and NR 630 Melt processing
<20 µm)
[24,25,125]
Melt compounding
Nylon 6 Miscanthus fiber 20 wt.% 500 and 900 and injection
molding
Extrusion and
Polypropylene Landfill pine wood 24 wt.% 900
injection molding
[40–43]
Mixed hardwood
Polylactic acid 2, 6 and 10 wt.% 800 Solvent casting
(<250 µm)
HDPE Rice husk 30–70 wt.% 500 Twin-screw extrusion [90]
Waste brewed coffee
PLA 1, 2.5, 5, and 7.5 wt.% 700 Solvent casting [123]
powder
Micro injection
Polypropylene Date palm waste 0–15 wt.% 700 and 900 [124]
molding
6, 12, 18, 24, and Twin-screw extrusion
Polypropylene Pine wood 450 [126]
30 wt.% and melt blending
Polylactic acid and Wood residue and
0, 10, 20 wt.% 550 Injection molding [127]
BIOPLAST GS2189 sewage sludge
Cashew nutshell
Polyester 5, 10, 15 wt.% 500 Resin casting [128]
waste
Pyrolyzed at 500
Landfill pinewood Extrusion and
Polypropylene 0, 15, 25, 30, 35 wt.% followed by [129]
waste injection molding
activation at 900
Micro twin-screw
HDPE Rice husk 10–70 wt.% 600 [130]
extruder
Grapevine (120 Compression
Polylactic acid 1–10 wt.% 500 [131]
mesh) molding
Bamboo waste 0–40, 0–20, and
Micro-injection
Polylactic acid biochar, aramid fiber, 0–20 wt.%, 500 [132]
molding
and silica respectively
150 ◦ C for 30 min
Fiber glass reinforced
Spruce wood pellets 0, 5, and 10 wt.% followed by 450 ◦ C Resin casting [133]
epoxy resin
for 30 min
Arhar stalks and Bael Hand lay-up
Epoxy 2, 4, and 6 wt.% 800 [111]
shell technique
Landfill pine sawdust 0–25, and 0–10 wt.%, 500 followed by
Polypropylene Twin-screw extrusion [134]
biochar and wool respectively activation at 900
Low viscosity epoxy
Maple tree (10 µm) 0, 1, 2, 4, and 20 wt.% 600 and 1000 Resin molding [135]
resin
Diglycidyl ether of RT-200 followed by
Coconut shell biochar 1–7, and 30 vol.%, Hand lay-up
bisphenol A based 200–500 followed by [136]
and C. urens fibers respectively technique
epoxy resin 500–800

Polymer composites with 4 wt.% biochar have shown high tensile strength and 180%
higher strength compared to neat polymers. Also, at 4 wt.% biochar, significant improve-
ment in thermal resistance is noticed in polymer epoxy composites [14,15]. Also, an
experimental trial highlighted the impact of different biochar loads on Young’s modulus
of biochar filler in polypropylene polymer composites as shown below in Figure 6. It
is concluded that the impact strength shows a massive increase once biochar loading in-
creases more than 25 wt.%. In addition, increasing the biochar filler by 5 wt.% have shown
improvement in tensile strength and hardness of polymer composites as well as thermal
resistance [111].
Polymers 2023, 15, 3981 19 of 32

As shown in Figure 9, optimum biochar loading in HDPE polymer composites to

improve impact strength are between 23 wt.% and 35 wt.% reaching high impact strength of
3000 J/m. Also, experimental investigations have shown that biochar loadings at 25 wt.% in
polypropylene polymer composites have the same tensile strength and modulus as similar
properties in wood composites but higher flexural properties [16,90].

Figure 9. Impact of biochar loads in polypropylene polymer composites in terms of Young’s modulus
and impact strength [12,50,137].

6.5. Effects of Biochar Particle Size and Loading on Polymer Composites

Polymer composites can be processed using extrusion and injection molding methods.
Biochar can be incorporated into polymer composites through grinding, milling, and extru-
sion techniques. The thermal treatment and operating temperature of biochar can affect its
porosity and mean particle size distribution, which in turn influences the behavior of the
polymer composite [122]. While biochar offers high thermal stability, composite enhancers
may be required to increase the mechanical mixing of biochar filler and polymer composite.
The mechanical and electrical performance of biochar fillers in polymer composites is also
influenced by the particle size and porosity of biochar. Different operating conditions
during biomass pyrolysis and carbonization can result in varying mean pore sizes, thermal
and electrical conductivity, and mean particle size and distribution [122].
Biochar loading affects the chemical, mechanical, and electrical properties of polymer
composites. The addition of biochar enhances thermal properties, such as increasing
the crystallization temperature, because the nucleation sites in biochar are available for
crystallization [15,116]. The addition of biochar also improves the mechanical performance
of polymer composites by transferring stress from the polymer matrix to the biochar filler,
increasing mechanical resistance and preventing failure. For instance, the addition of
35 wt.% biochar in polymer composites increased the tensile modulus up to 3.80 GPa [110].
The improvement of mechanical properties of polymer composites is caused by high
porosity in biochar, which causes stress transfer between the filler and the polymer matrix,
obstructing mechanical failure. Biochar obtained at lower pyrolysis temperatures improves
wettability and molecular affinity, lowers the friction coefficient, and enhances the bio-
compatibility of polymer composites [7,91]. The improvement of thermal conductivity in
Polymers 2023, 15, 3981 20 of 32

polymer composites is a result of the faster heat diffusion generated by the biochar and its
ability to tolerate higher strain before reaching the glass transition temperature (Tg ). The
highest tensile strength achieved by biochar in polymer composites is achieved at lower
loadings. In addition, the higher filler concentration and cross-linking of biochar increase
the brittle behavior of polymer composites. The addition of 2–4 wt.% of biochar loading in
polymer composites modifies the tensile behavior from brittle to ductile. With the addition
of 2 wt.% biochar, the tensile strength and elongation increase by 45% and 400%, respec-
tively [90,135]. Biochar in polymer composites improves the viscosity of the composites;
additionally, the biochar particle size has massive effects on the flow behavior and leads
to a severe increase in shear viscosity to around 5000 Pa-s [122]. Biochar with smaller
particle size diameter has shown lower viscosity compared to samples with large particle
diameters. At lower loadings, biochar improves the elasticity of polymer composites and
increases the stiffness and overall mechanical properties of polymer composites [116]. The
addition of optimal concentrations of biochar also improves the flame-retardant properties
of composites [138]. Table 5 presents a summary of different preparation methods for
biochar-based polymer composites, as well as their limitations and applications.
Polymers 2023, 15, 3981 21 of 32

Table 5. Different polymer filler materials and changes in properties as well as a preparation method.

Plasticizer/Hardener/
Polymer Type Polymer Blend Preparation Method Change in Properties References
Stabilizer/Compatibilizer
Catalytic chemical vapor
Glass temperature (Tg) increase
Polystyrene Single-wall carbon nanotubes Dimethyl; dibutyl deposition for CNTs; [139]
by 3 ◦ C
copolymerization for composite
Glass fiber; talc or calcium Glass temperature (Tg) increase
Poly(propylene carbonate) Nanoclay at 4 wt.% Co-polymerization [25,26,139]
carbonate by 13 ◦ C
Co-polymerization of CO2 and Glass temperature decreases by
Polylactide Naoclay at 3 wt.% [55,67–71,73–95,140,141]
chemicals called epoxides 4 ◦C
Glass temperature increases by
Rubber Nanoclay at 5 wt.% Adipates and Sebacates Triethyl citrate or tributyl citrate [94–104]
3 ◦C
Pyrolysis and carbonization for
Higher glass temperature; higher
Glass-fiber-reinforced composites Biochar at 5 wt.% to 10 wt.% Organic esters biochar; extrusion for polymer [12–14,84,142,143]
stiffness and fire retardancy
composite
Silica pore size between 2 nm and Higher glass temperature at
Poly(dimethyl siloxane) Trimethylsiloxy-terminated Replica molding or casting [12–14,84,142,143]
3 nm 10 ◦ C
High-purity silica at 30%
Present good homogeneous and
(average particle size = 3, 6, 16,
effective bond between matrix
and 22 µm), 10% (average methyl-ethyl-ketone-peroxide
Unsaturated polyester resin Molding or casting and particles; hardness and [144]
particle size = 0.1, 1, 2, 3, 6, 16, (MEKPO)
elastic modulus increases linearly
and 22 µm), 12%, 16%, 24%, 37%,
with filler content
and 46% filler volume
Tensile strength of the composite
decreases with increased filler
Rice husks at 10, 15, 20, and methyl-ethyl-ketone-peroxide loading; Young’s modulus
Unsaturated polyester Room-temperature molding [145]
25 wt.% (MEKPO) increased remarkably for
15 wt.%; the composite showed
higher water absorption
Graphene-based flakes are
Lower filler content increases the
Graphene-based flakes (average prepared using
Semi-crystalline LDPE, and two viscosity; glass transition
flake size = 1.45 µm); fumed micro-fluidization; polymer
amorphous (polystyrene and temperature showed mixed [91]
silica (average particle size = composite using extrusion
polymethyl methacrylate) behavior, e.g.,
0.2–0.3 µm) melt-mixing followed by
increasing/decreasing nature
injection molding
Polymers 2023, 15, 3981 22 of 32

Table 5. Cont.

Plasticizer/Hardener/
Polymer Type Polymer Blend Preparation Method Change in Properties References
Stabilizer/Compatibilizer
15 wt.% composite showed
improved wear resistance and
Epoxy belong to diglycidyl ether
Potassium titanate whisker Mechanical stirring and highest friction coefficient;
of bisphenol A Amino based [146]
(PTW) with aspect ratio 20–40 vacuum-assisted casting method positive effect on hardness,
(DGEBA) family
density, and stiffness. But the
strength and ductility decreases
Increases glass transition
temperature, storage, and elastic
Polyvinyl chloride (PVC) of Calcium Carbonate (CaCO3 ) in Melt-blended in twin-screw modulus; however, reduces
Arkopan [147]
density 1.41 g/cm3 1–2 µm particle size extruder tensile strength and elongation at
break and no significant effect on
water absorption
Increased filler content improves
filler–filler interaction;
agglomeration of wood particles
Maleic anhydride-modified
which increases storage modulus
High-density polyethylene Poplar wood flour sieved polyethylene with melt index 6
Twin-screw extrusion and viscosity of the composite [148]
(HDPE) of different grades through 60 mesh g/10 min, and a graft ratio of
with decreased tensile strength;
1.1%
elongation at break; notched
impact strength due to stress
concentration
Steep increase in impact strength
Flyash (Class-F) with density 2
Glass fibers reinforced is noted for small filler content;
g/cc and total silica and alumina Hardener HY951 Resin molding [149]
low-temperature curing epoxy compressive strength found to be
content > 70%
decreasing
Increased filler level enhances
compressive strength, hardness,
stiffness with reduced water
Silanated barium borosilicate
absorption; all the resins showed
Visible-light-activated with particle size 2 µm (at 20, 40,
significant improvement in
polyphenylene polymethacrylate 45, 50, and 53 vol% loading) and [43]
resistance to wear by
resin 15 µm (at 20, 40, 50, 60, and 65
hydroxyapatite than unfilled
vol% loading)
resins; however, particle sizes of
filler have moderate impact on
the resin properties
Polymers 2023, 15, 3981 23 of 32

6.6. Effects of Biochar Surface Area

Surface modification of biochar can help remove impurities and improve adhesion
with the matrix interface, leading to enhanced mechanical properties in polymer composites.
Varying the biochar filler loading can also affect the mechanical properties and stiffness
of the polymer matrix, as observed through indentation testing. The high surface area of
biochar can improve the reinforcement and mechanical interlocking of polymers, which
can be predicted using the Halpin–Tsai–Nielsen and Verbeek models [43,150,151]. Higher
biochar loads can also increase polymer matrix hardness, with biochar produced at higher
operating temperatures generally resulting in higher surface area and improved mechanical
strength and hardness of polymer composites [90].

6.7. Effects of Biomass Feedstock Properties on the Quality of Biochar

The choice of technology used to produce biochar has a significant impact on its
effectiveness as a filler in polymer composites, as shown in experimental investigations.
Factors such as the production operating temperature, the reactor design, and the feedstock
used can affect the biochar’s porosity and mechanical properties [111]. Additionally, biochar
derived from wood has been found to have higher mechanical and tensile strength when
used as a reinforcement material. For instance, a composite made with Bael shell biochar at
a 4 wt.% loading exhibited 180% higher tensile strength compared to virgin polymers [111].
Moreover, increasing the biochar filler percentage from 4% to 6% led to an increase in
composite stiffness, hardness, and thermal resistance [46,47,152,153]. Biochar originating
from pine wood, generated at a temperature of 500 ◦ C and subsequently subjected to
activation at 900 ◦ C, has been employed in polypropylene composites to enhance their
mechanical characteristics [9].
Residual biomass-derived biochar can enhance the thermal and acoustic properties
of concrete, with thermal annealing of biochar up to 1500 ◦ C further improving thermal
properties [154]. When added to polymer composites, biochar can improve mechanical
properties by facilitating stress release and transfer between filler and polymer compos-
ite [90]. Biochar’s stability, high electrical conductivity, low thermal conductivity, and high
chemical stability and can reduce the flammability of polymer composites. Incorporating
biochar in polymer composites decreases dependent thermal conductivity in composites,
and the carbon content during carbonization affects thermal conductivity. For example,
increasing the carbon content from 85 to 94 wt.% results in an increase in the order of
magnitude of the bulk conductivity by 6 [18]. Compression of biochar increases electri-
cal conductivity through the elastic behavior of electrically conductive biochar [18]. The
porosity of biochar, which is affected by the pyrolysis operating temperature, heating rate,
and biomass feedstock, also affects electrical conductivity. Higher operating temperatures
result in biochar with higher electrical conductivity, with biochar produced from biomass
pyrolysis at 700 ◦ C exhibiting greater electrical conductivity due to higher surface area and
lower porosity than that produced at 500–600 ◦ C. Table 6 presents a summary of the factors
which influence the properties of biochar.

6.8. Surface Interactions of Biochar Particles and Biochar Matrix in Polymer Composites
When biochar is added to the polymer matrix in the interfacial region, the surface
morphology and viscoelastic properties of the polymer composite can be measured by
Young’s modulus for the biochar–polymer composite. The addition of biochar decreases
the polymer–polymer chain interactions and reduce the elastic properties of the polymer
composite [30]. The selection of high pyrolysis temperatures produces more porous biochar
depending on the feedstock type used; the characteristics of the biochar’s intra-pores
change with different operating temperatures and residence times. Therefore, optimal
charring temperatures and residence times should be specified to produce biochar with
high intra-porosity [155]. The addition of biochar particles, assessed using nano-hardness
values and Young’s modulus, have shown higher flexural strength up to 35% compared to
conventional glass-fiber-reinforced polymers (GFRP); this also showed a lower Young’s
Polymers 2023, 15, 3981 24 of 32

modulus, which was reduced by 35% [133]. The surface morphology characteristics of
the biochar were significantly impacted by both the source material and the temperature
used during pyrolysis. The fibrous structures present in sawdust and furfural residue were
preserved in their respective biochar samples, constituting the carbon framework within
these biochar samples. Mesoporous biochar with a high surface area (1493 m2 . g−1 ) is
obtained at optimized conditions.

Table 6. Summary of influential factors and their impact on biochar product yield.

Influential Factor Description Biochar Product Yield References

High biochar yield based on
Lignin content has an impact on lignin content with low surface
Lignin weight content of biomass
biochar yield and fixed carbon area; high surface PH and
feedstock
content functional groups; high ion
exchange capacity.
The inorganic content increases,
biochar yield through bond
Inorganic content weight dissociation energy between
[2,22,71,76,78,86]
Influence of inorganic content percentage has an impact on organic and inorganic carbon
biochar properties increases; higher electrical
conductivity and loss of
volatile matter.
Higher surface area of biochar
and higher pore volume with
Low product yield of biochar;
Higher operating temperature in stronger mechanical properties;
high fixed carbon and lower
thermochemical reactions higher PH and electrical
volatile matter
conductivity; high crushing and
impact strengths of biochar.

Functionalizing the surface of biochar can be achieved through the use of oxidizing
agents like nitric acid, which increases the presence of oxygen surface-functional groups.
While several studies have reported successful biochar surface functionalization with nitric
acid, this process typically demands extended periods and the use of highly concentrated
nitric acid. Moreover, this functionalization process tends to impact the morphology and
pore structure of the modified carbon material, resulting in a reduction in the surface area.
These reductions in surface area, coupled with the use of concentrated caustic chemicals
and the time involved, present obstacles to implementing this functionalization process in
industrial settings due to associated hazards and costs [156].
To address this issue, a functionalization process employing an autoclave is proposed,
as these are readily available in palm oil mills for sterilization purposes. This method
is suggested to expedite biochar functionalization, thereby enhancing biochar surface
functionalities and, subsequently, its adsorption performance. The differentiating factor
between the autoclave method and other reported modification techniques lies in the
combination of elevated temperature and pressure during treatment. By offering multiple
oxidation pathways, this approach is expected to significantly improve the efficiency of the
process [157]. Addition of biochar improved the mechanical and thermal interactions of
polymer composites in starch–biochar polymer matrixes. Hydrophobic biochar exhibits a
positive water entry pressure, indicating that an external force is necessary to allow water to
penetrate its intra-pores. In the absence of this external force, water cannot enter the intra-
pores, leading to the prevention of intra-pore saturation and limiting the water-retention
benefits of biochar [90]. Jeffery et al. noted that biochar derived from grass species did not
enhance soil water retention, likely due to its high hydrophobicity (with an average contact
angle of 118◦ ). It is worth mentioning that grass biochar, while hydrophobic, still has lower
hydrophobicity when compared to leaf or wood biochar. The degree of hydrophobicity
in biochar varies depending on the production temperature and the feedstock used, but
it is typically eliminated through brief exposure to the environment. Pre-treating biochar,
either by initially wetting it or through composting, is likely to significantly mitigate issues
associated with hydrophobicity [158].
Polymers 2023, 15, 3981 25 of 32

6.9. Economic Feasibility of Biochar in Polymer Composites

The economic feasibility of using biochar in polymer composites depends on various
factors, including the cost of biochar production, the performance improvement it offers
to the composites, and the potential market demand for such eco-friendly materials [84].
These factors are described briefly in this section.
Biochar Production Costs: The cost of producing biochar can vary significantly depend-
ing on the feedstock used, the production method, and the scale of production. Commonly
recommended feedstocks for biochar production include agricultural residues, wood waste,
and organic waste materials. Generally, biochar may cost between USD 222 and USD 584
per ton to produce, deliver, and spread on fields [159]. However, the cost associated with
transportation of biochar, the related equipment purchase, thermochemical conversion
process, and high dosage use makes agricultural and environmental uses of biocarbon
infeasible [160]. Therefore, it is crucial to assess the local availability of feedstock and the
efficiency of the production process to determine the cost of biochar.
Performance Enhancement: Biochar can be added to polymer composites to enhance
their mechanical, thermal, and environmental properties. This enhancement may reduce
the amount of expensive polymer material required to achieve the same performance,
potentially offsetting the cost of biochar. However, the extent of performance improve-
ment and the resulting reduction in polymer usage should be evaluated in terms of their
economic impacts.
Market Demand: The global market demand for biochar-based polymer composites is
a critical factor. If there is a growing trend toward sustainable and eco-friendly materials
in various industries (e.g., construction, automotive, and packaging industries), then it
might create a favorable market for biochar composites. The willingness of consumers and
businesses to be adaptable and to potentially pay a premium for eco-friendly products can
also affect the economic feasibility.
Regulatory and Certification Costs: Depending on the region and industry, there may
be regulatory requirements or certifications associated with the use of biochar in polymer
composites. Compliance with these standards may add to the overall cost of production
and should be considered in economic feasibility assessments.
Competitive Pricing: To determine economic feasibility, it is essential to compare the
cost of biochar-based polymer composites to existing alternatives. If the price of traditional
polymer composites is significantly lower, it may be challenging to gain market traction
unless there are other compelling benefits. However, several countries have started to
offer carbon tax benefits to industries producing and utilizing biocarbon products as an
incentive for reducing their carbon footprints; accordingly, the reduction in costs pertaining
to biochar-based polymer composites and the enhancement of their properties should
be considered.
Long-term Benefits: The long-term benefits of using biochar, such as potential cost
savings from reduced polymer usage, extended product lifespan, and lower environmental
impact should be considered. These factors can positively influence economic feasibility
over time, which is a factor which could be used to encourage consumer adaptability.
Research and Development Costs: There may be research and development costs
to consider when assessing the costs related to the development of novel biochar-based
polymer composites. These costs can impact initial economic feasibility assessments, but
may lead to competitive advantages in the future.
Considering aforementioned factors, the economic feasibility of using biochar in
polymer composites is a complex issue that depends on multiple factors; it is essential to
determine whether the use of biochar in polymer composites makes economic sense in
a specific application or industry. Additionally, staying informed about evolving market
trends and consumer preferences for sustainable materials is crucial for making informed
decisions [158–160].
Polymers 2023, 15, 3981 26 of 32

7. Research Gap and Future Prospective

Biochar is a sustainable and organic filler that can enhance the properties of poly-
mer matrices. However, there is a research gap in several aspects of biochar usage as
a re-enforcement material. To develop biochar with optimal mechanical properties and
electrical conductivity, high thermal control is necessary for pyrolizers. Further studies are
required to analyze the improvement of mechanical, thermal, and acoustic properties at
different biochar loads and investigate the impact of biochar particle size and morphology
on the mechanical properties of polymer composites. The optimal biochar loadings that
increase the glass transition temperature and the thermal stability of composites need to be
investigated. Moreover, the morphology of biochar requires investigation to deter-mine its
effects on stiffness and fire-resistant properties. The optimal biochar loads that achieve high
storage modulus and better dispersion in a polymer matrix need to be determined. The
effects of biochar loading that improve flame retardancy properties are also yet to be inves-
tigated. Future research topics include the development of pyrolizers that can achieve high
thermal control and control over biochar particle size and morphology. Furthermore, under-
standing how filler morphology affects biochar properties and its impact on the electrical
conductivity of polymer composites is crucial. Ultimately, further studies are necessary to
optimize the use of biochar as a sustainable and effective filler in polymer composites.

8. Conclusions
Biochar has emerged as a promising additive for polymer composites, offering signifi-
cant improvements for their thermal, mechanical, and electrical properties. Compared to
other fillers, biochar demonstrates superior thermal stability. It is lightweight, easy to fabri-
cate, and cost-effective, making it an attractive option for weight reduction in automobiles.
The addition of ions to biochar further enhances the electrical conductivity of polymer
composites. To achieve the optimal improvement in mechanical properties, a 10 wt.%
biochar addition is recommended; as biochar content increases beyond this threshold, the
mechanical properties of polymer composites tend to deteriorate. For biochar to be effective,
it should possess high surface area and porosity, high cation exchange capacity (CEC),
neutral–high PH, and a high carbon mass ratio. Optimal biochar properties and surface
area are achieved at higher operating temperatures during pyrolysis and carbonization.
Biochar produced at temperatures above 1000 ◦ C demonstrates higher electrical conduc-
tivity. Biochar compression also increases electrical conductivity in polymer composites.
Studies are necessary to evaluate the toxicity and the thermal and mechanical stability of
biochar in various polymer composites, and to assess its suitability for diverse industrial
applications. Overall, biochar shows promise as a sustainable organic filler with exceptional
physical properties.

Author Contributions: M.A.: conceptualization, literature review, writing—original draft, writing—

review and editing, visualization. A.B.-G.: writing—structural editing, review and editing, visualiza-
tion. P.D.: Literature review, writing—review and editing. R.P.: Literature review, writing—review
and editing. B.A.: conceptualization, supervision, funding acquisition, writing—review and editing,
resources. All authors have read and agreed to the published version of the manuscript.
Funding: The work was supported by Natural Science and Engineering Research Council Discovery
Grant program [RGPIN-2022-05111] and Saskatchewan Ministry of Agriculture Research Chair Funds.
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Funding from Canada Foundation for Innovation, Natural Sciences and En-
gineering Research Council of Canada and the University of Saskatchewan support research at
the SSSC.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2023, 15, 3981 27 of 32

Glossary

Symbols
Hm Sample melting enthalpy
Pa-s Pascal second (Pa-s)
S/cm Siemens per centimeter
TPA Tera pascal (elastic modulus)
Abbreviations
CFRP Carbon-fiber-reinforced polymer
MWCNTs Multi-walled carbon nanotubes

References
1. Štefanko, A.U.; Leszczynska, D. Impact of Biomass Source and Pyrolysis Parameters on Physicochemical Properties of Biochar
Manufactured for Innovative Applications. Front Energy Res. 2020, 8, 138. [CrossRef]
2. Bartoli, M.; Giorcelli, M.; Jagdale, P.; Rovere, M. Towards Traditional Carbon Fillers: Biochar-Based Reinforced Plastic. In Fillers;
IntechOpen: London, UK, 2021. [CrossRef]
3. Lin, Q.; Tan, X.; Almatrafi, E.; Yang, Y.; Wang, W.; Luo, H.; Qin, F.; Zhou, C.; Zeng, G.; Zhang, C. Effects of biochar-based materials
on the bioavailability of soil organic pollutants and their biological impacts. Sci. Total Environ. 2022, 826, 153956. [CrossRef]
4. Li, S.; Xu, Y.; Jing, X.; Yilmaz, G.; Li, D.; Turng, L.S. Effect of carbonization temperature on mechanical properties and biocompati-
bility of biochar/ultra-high molecular weight polyethylene composites. Compos. B Eng. 2020, 196, 108120. [CrossRef]
5. Tan, R.R.; Aviso, K.B.; Bandyopadhyay, S. Pinch-based planning of terrestrial carbon management networks. Clean Eng. Technol.
2021, 4, 100141. [CrossRef]
6. Zoghlami, A.; Paës, G. Lignocellulosic biomass: Understanding recalcitrance and predicting hydrolysis. Front. Chem. 2019, 7, 874.
[CrossRef] [PubMed]
7. Rothon, R. Fillers for Polymer Applications; Springer: Berlin/Heidelberg, Germany, 2017. [CrossRef]
8. Harper, C.A. Handbook of Plastics, Elastomers, and Composites, Technology; McGraw-Hill Education: New York, NY, USA, 2002.
9. Haeldermans, T.; Campion, L.; Kuppens, T.; Vanreppelen, K.; Cuypers, A.; Schreurs, S. A comparative techno-economic
assessment of biochar production from different residue streams using conventional and microwave pyrolysis. Bioresour. Technol.
2020, 318, 124083. [CrossRef] [PubMed]
10. Sobhan, A.; Muthukumarappan, K.; Wei, L.; Qiao, Q.; Rahman, M.T.; Ghimire, N. Development and characterization of a novel
activated biochar-based polymer composite for biosensors. Int. J. Polym. Anal. Charact. 2021, 26, 544–560. [CrossRef]
11. Frontini, P.M.; Pouzada, A.S. Trends in the multifunctional performance of polyolefin/clay nanocomposite injection moldings. In
Multifunctionality of Polymer Composites: Challenges and New Solutions; William Andrew: Norwich, NY, USA, 2015. [CrossRef]
12. Park, S.; Fu, K. Polymer-based filament feedstock for additive manufacturing. Compos. Sci. Technol. 2021, 213, 108876. [CrossRef]
13. Ma, P.C.; Siddiqui, N.A.; Marom, G.; Kim, J.K. Dispersion and functionalization of carbon nanotubes for polymer-based
nanocomposites: A review. Compos. Part A Appl. Sci. Manuf. 2010, 41, 1345–1367. [CrossRef]
14. Bajpai, P.K.; Singh, I. Reinforced Polymer Composites: Processing, Characterization and Post Life Cycle Assessment; John Wiley & Sons:
Hoboken, NJ, USA, 2019. [CrossRef]
15. DeArmitt, C.; Rothon, R.; Fillers, P. Selection, and Use in Polymer Composites. In Polymers and Polymeric Composites: A Reference
Series; Springer: Berlin/Heidelberg, Germany, 2016. [CrossRef]
16. Vivekanandhan, S. Biochar as Sustainable Reinforcement for Polymer Composites. In Encyclopedia of Renewable and Sustainable
Materials; Elsevier: Amsterdam, The Netherlands, 2020. [CrossRef]
17. Poulose, A.M.; Elnour, A.Y.; Anis, A.; Shaikh, H.; Al-Zahrani, S.M.; George, J.; Al-Wabel, M.I.; Usman, A.R.; Ok, Y.S.; Tsang,
D.C.W.; et al. Date palm biochar-polymer composites: An investigation of electrical, mechanical, thermal and rheological
characteristics. Sci. Total Environ. 2017, 619, 311–318. [CrossRef]
18. Gabhi, R.S.; Kirk, D.W.; Jia, C.Q. Preliminary investigation of electrical conductivity of monolithic biochar. Carbon 2017, 116,
435–442. [CrossRef]
19. Kane, S.; Warnat, S.; Ryan, C. Improvements in methods for measuring the volume conductivity of electrically conductive carbon
powders. Adv. Powder Technol. 2021, 32, 702–709. [CrossRef]
20. Khan, A.; Savi, P.; Quaranta, S.; Rovere, M.; Giorcelli, M.; Tagliaferro, A.; Rosso, C.; Jia, C.Q. Low-cost carbon fillers to improve
mechanical properties and conductivity of epoxy composites. Polymers 2017, 9, 642. [CrossRef]
21. Das, C.; Tamrakar, S.; Mielewski, D.; Kiziltas, A.; Xie, X. Newly developed biocarbon to increase electrical conductivity in
sustainable polyamide 12 composites. Polym. Compos. 2022, 43, 8084–8094. [CrossRef]
22. Lepak-Kuc, S.; Kiciński, M.; Michalski, P.P.; Pavlov, K.; Giorcelli, M.; Bartoli, M.; Jakubowska, M. Innovative biochar-based
composite fibres from recycled material. Materials 2021, 14, 5304. [CrossRef] [PubMed]
23. Faga, M.G.; Duraccio, D.; Di Maro, M.; Pedraza, R.; Bartoli, M.; d’Ayala, G.G.; Torsello, D.; Ghigo, G.; Giulio, M.; Acetate, E.-V.
Electrical, Thermal and Tribological Behavior. Polymers 2022, 14, 4171. [CrossRef]
24. Kane, S.; Ulrich, R.; Harrington, A.; Stadie, N.P.; Ryan, C. Physical and chemical mechanisms that influence the electrical
conductivity of lignin-derived biochar. Carbon Trends 2021, 5, 100088. [CrossRef]
Polymers 2023, 15, 3981 28 of 32

25. Dreyfuss, P.; Hansen, D.R.; Fetters, L.J. Elastomeric Block Polymers. Rubber Chem. Technol. 1980, 53, 728–771. [CrossRef]
26. Sardar, M.; Arun, R.K.; Ige, E.O.; Singh, P.; Kumar, G.; Chanda, N.; Biswas, G. Sustainable Polymer-Based Microfluidic Fuel
Cells for Low-Power Applications. In Advances in Sustainable Polymers: Processing and Applications; Springer: Berlin/Heidelberg,
Germany, 2019. [CrossRef]
27. Benkhelladi, A.; Laouici, H.; Bouchoucha, A. Tensile and flexural properties of polymer composites reinforced by flax, jute and
sisal fibres. Int. J. Adv. Manuf. Technol. 2020, 108, 895–916. [CrossRef]
28. Sun, F.; Tian, M.; Sun, X.; Xu, T.; Liu, X.; Zhu, S.; Zhang, X.; Qu, L. Stretchable Conductive Fibers of Ultrahigh Tensile Strain and
Stable Conductance Enabled by a Worm-Shaped Graphene Microlayer. Nano Lett. 2019, 19, 6592–6599. [CrossRef]
29. Singh, K.K.; Chaudhary, S.K.; Venugopal, R. Enhancement of flexural strength of glass fiber reinforced polymer laminates using
multiwall carbon nanotubes. Polym. Eng. Sci. 2019, 59, E248–E261. [CrossRef]
30. George, J.; Azad, L.B.; Poulose, A.M.; An, Y.; Sarmah, A.K. Nano-mechanical behaviour of biochar-starch polymer composite:
Investigation through advanced dynamic atomic force microscopy. Compos. Part A Appl. Sci. Manuf. 2019, 124, 105486. [CrossRef]
31. Abeykoon, C.; Kelly, A.L.; Vera-Sorroche, J.; Brown, E.C.; Coates, P.D.; Deng, J.; Li, K.; Harkin-Jones, E.; Price, M. Process efficiency
in polymer extrusion: Correlation between the energy demand and melt thermal stability. Appl. Energy 2014, 135, 560–571.
[CrossRef]
32. Abeykoon, C.; Kelly, A.L.; Brown, E.C.; Vera-Sorroche, J.; Coates, P.D.; Harkin-Jones, E.; Howell, K.B.; Deng, J.; Li, K.; Price, M.
Investigation of the process energy demand in polymer extrusion: A brief review and an experimental study. Appl. Energy 2014,
136, 726–737. [CrossRef]
33. Nastaj, A.; Wilczyński, K. Optimization and scale-up for polymer extrusion. Polymers 2021, 13, 1547. [CrossRef]
34. Wilczyński, K.; Nastaj, A.; Lewandowski, A.; Wilczyński, K.K.; Buziak, K. Fundamentals of global modeling for polymer extrusion.
Polymers 2019, 11, 2106. [CrossRef]
35. Vera-Sorroche, J.; Kelly, A.; Brown, E.; Coates, P.; Karnachi, N.; Harkin-Jones, E.; Li, K.; Deng, J. Thermal optimisation of polymer
extrusion using in-process monitoring techniques. Appl. Therm. Eng. 2013, 53, 405–413. [CrossRef]
36. Demay, Y.; Agassant, J.F. The Polymer Film Casting Process—An Overview. Int. Polym. Process. 2021, 36, 264–275. [CrossRef]
37. Koomen, M. Using Polymer Solution Casting to Deliver High-Quality Films, Carestream Contract Manufacturing: Precision
Custom Coating Services. Bachelor’s Thesis, Tampere University, Tampere, Finland, 2015.
38. Xie, M.; Zhang, Y.; Kraśny, M.J.; Bowen, C.; Khanbareh, H.; Gathercole, N. Flexible and active self-powered pressure, shear
sensors based on freeze casting ceramic-polymer composites. Energy Environ. Sci. 2018, 11, 2919–2927. [CrossRef]
39. Rokade, D.; Patil, P.; Nandimath, S.; Pol, H. A rheology and processing study on controlling material and process defects in
polymer melt extrusion film casting using polymer blends. J. Plast. Film. Sheeting 2023, 39, 211–240. [CrossRef]
40. Rosenblum, J.S.; Cappadona, A.J.; Lookian, P.P.; Chandrashekhar, V.; Bryant, J.P.; Chandrashekhar, V.; Zhao, D.Y.; Knutsen, R.H.;
Donahue, D.R.; McGavern, D.B.; et al. Non-invasive in situ visualization of the murine cranial vasculature. Cell Rep. Methods
2022, 2, 100151. [CrossRef] [PubMed]
41. Zajac, J.; Petruska, O.; Radchenko, S.; Duplakova, D.; Goldyniak, D. Hardness testing of polymer concrete castings by Schmidt
hammer. Mater. Today Proc. 2020, 22, 293–299. [CrossRef]
42. Mu, Y.; Hang, L.; Zhao, G.; Wang, X.; Zhou, Y.; Cheng, Z. Modeling and simulation for the investigation of polymer film casting
process using finite element method. Math. Comput. Simul. 2019, 169, 88–102. [CrossRef]
43. Huang, S.; Fu, Q.; Yan, L.; Kasal, B. Characterization of interfacial properties between fibre and polymer matrix in composite
materials—A critical review. J. Mater. Res. Technol. 2021, 13, 1441–1484. [CrossRef]
44. Mohammed, M.; Rasidi, M.S.M.; Mohammed, A.M.; Rahman, R.; Osman, A.F.; Adam, T.; Betar, B.O.; Dahham, O.S. Interfacial
Bonding Mechanisms of Natural Fibre-Matrix Composites: An Overview. Bioresources 2022, 17, 7031. [CrossRef]
45. Lee, C.H.; Khalina, A.; Lee, S.H. Importance of interfacial adhesion condition on characterization of plant-fiber-reinforced polymer
composites: A review. Polymers 2021, 13, 438. [CrossRef]
46. Babu, K.; Rendén, G.; Mensah, R.A.; Kim, N.K.; Jiang, L.; Xu, Q.; Restás, A.; Neisiany, R.E.; Hedenqvist, M.S.; Försth, M.; et al. A
Review on the Flammability Properties of Carbon-Based Polymeric Composites: State-of-the-Art and Future Trends. Polymers
2020, 12, 1518. [CrossRef]
47. Infurna, G.; Caruso, G.; Dintcheva, N.T. Sustainable Materials Containing Biochar Particles: A Review. Polymers 2023, 15, 343.
[CrossRef]
48. Danglad-Flores, J.; Eickelmann, S.; Riegler, H. Deposition of polymer films by spin casting: A quantitative analysis. Chem. Eng.
Sci. 2018, 179, 257–264. [CrossRef]
49. Zheng, W.; Hu, Y.; Zhang, X. Recent progress in synthesis of stereoblock copolymers. Kexue Tongbao/Chin. Sci. Bull. 2016, 61,
3651–3660. [CrossRef]
50. Guggari, G.S.; Shivakumar, S.; Manjunath, G.A.; Nikhil, R.; Karthick, A.; Edacherian, A.; Saleel, C.A.; Afzal, A.; Prasath, S.; Saleh,
B. Thermal and Mechanical Properties of Vinyl Ester Hybrid Composites with Carbon Black and Glass Reinforcement. Adv. Mater.
Sci. Eng. 2021, 2021, 1–7. [CrossRef]
51. Wolff, S.; Wang, M.-J. Carbon Black Filler Reinforcement of Elastomers. In Carbon Black: Science and Technology; Routledge:
Oxfordshire, UK, 1993.
52. Spahr, M.E.; Rothon, R. Carbon Black as a Polymer Filler. In Polymers and Polymeric Composites: A Reference Series; Springer:
Berlin/Heidelberg, Germany, 2016. [CrossRef]
Polymers 2023, 15, 3981 29 of 32

53. Fan, Y.; Fowler, G.D.; Zhao, M. The past, present and future of carbon black as a rubber reinforcing filler—A review. J. Clean. Prod.
2019, 247, 119115. [CrossRef]
54. Fukahori, Y. The mechanics and mechanism of the carbon black reinforcement of elastomers. Rubber Chem. Technol. 2003, 76,
548–566. [CrossRef]
55. Branco-Vieira, M.; Mata, T.; Martins, A.; Freitas, M.; Caetano, N. Economic analysis of microalgae biodiesel production in a
small-scale facility. Energy Rep. 2020, 6, 325–332. [CrossRef]
56. Adohi, B.J.P.; Mdarhri, A.; Prunier, C.; Haidar, B.; Brosseau, C. A comparison between physical properties of carbon black-polymer
and carbon nanotubes-polymer composites. J. Appl. Phys. 2010, 108, 074108. [CrossRef]
57. Goh, P.S.; Ismail, A.F.; Ng, B.C. Directional alignment of carbon nanotubes in polymer matrices: Contemporary approaches and
future advances. Compos. Part A Appl. Sci. Manuf. 2014, 56, 103–126. [CrossRef]
58. Bokobza, L.; Pflock, T.; Lindemann, A.; Kwiryn, D.; Claro, P.D.S. Thermal conductivity and mechanical properties of composites
based on multiwall carbon nanotubes and styrenebutadiene rubber. KGK Kautsch. Gummi Kunststoffe 2014, 67, 45–50.
59. Wang, Y.; Cai, N.; Yang, H.; Wu, C. Application of Carbon Nanotubes from Waste Plastics as Filler to Epoxy Resin Composite.
ACS Sustain. Chem. Eng. 2022, 10, 2204–2213. [CrossRef]
60. Dhilipkumar, T.; Rajesh, M. Effect of manufacturing processes and multi-walled carbon nanotube loading on mechanical and
dynamic properties of glass fiber reinforced composites. Polym. Compos. 2022, 43, 1772–1786. [CrossRef]
61. Nuyang, P.; Wiriya-Amornchai, A.; Cheewawuttipong, W. The effects of a compatibilizer for improving mechanical properties on
polymer matrix composites. Key Eng. Mater. 2021, 877, 3–8. [CrossRef]
62. Zhang, M.; Zhai, Z.; Li, M.; Cheng, T.; Wang, C.; Jiang, D.; Chen, L.; Wu, Z.; Guo, Z. Epoxy nanocomposites with carbon nanotubes
and montmorillonite: Mechanical properties and electrical insulation. J. Compos. Mater. 2016, 50, 3363–3372. [CrossRef]
63. Ke, K.; McMaster, M.; Christopherson, W.; Singer, K.D.; Manas-Zloczower, I. Effects of branched carbon nanotubes and graphene
nanoplatelets on dielectric properties of thermoplastic polyurethane at different temperatures. Compos. Part B Eng. 2019, 166,
673–680. [CrossRef]
64. Savi, P.; Josè, S.P.; Khan, A.A.; Giorcelli, M.; Tagliaferro, A. Biochar and carbon nanotubes as fillers in polymers: A comparison. In
Proceedings of the 2017 IEEE MTT-S International Microwave Workshop Series on Advanced Materials and Processes for RF and
THz Applications, IMWS-AMP 2017, Chengdu, China, 20–22 September 2018. [CrossRef]
65. Kozlov, G.V.; Magomedov, G.M.; Magomedov, G.M.; Dolbin, I.V. The structure of carbon nanotubes in a polymer matrix. Kondens.
Sredy I Mezhfaznye Granitsy = Condens. Matter Interphases 2021, 23, 223–228. [CrossRef]
66. Horst, J.D.; De Andrade, P.P.; Duvoisin, C.A.; Vieira, R.D. Fabrication of Conductive Filaments for 3D-printing: Polymer
Nanocomposites. Biointerface Res. Appl. Chem. 2020, 10, 6577–6586. [CrossRef]
67. Hollaway, L.C. Key issues in the use of fibre reinforced polymer (FRP) composites in the rehabilitation and retrofitting of concrete
structures. In Service Life Estimation and Extension of Civil Engineering Structures; Woodhead Publishing: Cambridge, UK, 2010.
68. Chung, D. Comparison of submicron-diameter carbon filaments and conventional carbon fibers as fillers in composite materials.
Carbon 2001, 39, 1119–1125. [CrossRef]
69. Idrees, M.; Jeelani, S.; Rangari, V. Three-Dimensional-Printed Sustainable Biochar-Recycled PET Composites. ACS Sustain. Chem.
Eng. 2018, 6, 13940–13948. [CrossRef]
70. Noori, A.; Bartoli, M.; Frache, A.; Piatti, E.; Giorcelli, M.; Tagliaferro, A. Development of Pressure-Responsive PolyPropylene and
Biochar-Based Materials. Micromachines 2020, 11, 339. [CrossRef]
71. Elnour, A.Y.; Alghyamah, A.A.; Shaikh, H.M.; Poulose, A.M.; Al-Zahrani, S.M.; Anis, A.; Al-Wabel, M.I. Effect of Pyrolysis
Temperature on Biochar Microstructural Evolution, Physicochemical Characteristics, and Its Influence on Biochar/Polypropylene
Composites. Appl. Sci. 2019, 9, 1149. [CrossRef]
72. Al Habis, N.; El Moumen, A.; Tarfaoui, M.; Lafdi, K. Mechanical properties of carbon black/poly (ε-caprolactone)-based tissue
scaffolds. Arab. J. Chem. 2018, 13, 3210–3217. [CrossRef]
73. Biron, M. Recycling Plastics: Advantages and Limitations of Use. In A Practical Guide to Plastics Sustainability; Elsevier: Amsterdam,
The Netherlands, 2020. [CrossRef]
74. Wallace, C.A.; Saha, G.C.; Afzal, M.T.; Lloyd, A. Experimental and computational modeling of effective flexural/tensile properties
of microwave pyrolysis biochar reinforced GFRP biocomposites. Compos. Part B Eng. 2019, 175, 107180. [CrossRef]
75. Ibrahim, A.; Klopocinska, A.; Horvat, K.; Hamid, Z.A. Graphene-Based Nanocomposites: Synthesis, Mechanical Properties, and
Characterizations. Polymers 2021, 13, 2869. [CrossRef]
76. Li, S.; Huang, A.; Chen, Y.-J.; Li, D.; Turng, L.-S. Highly filled biochar/ultra-high molecular weight polyethylene/linear low
density polyethylene composites for high-performance electromagnetic interference shielding. Compos. Part B Eng. 2018, 153,
277–284. [CrossRef]
77. Ji, X.; Xu, Y.; Zhang, W.; Cui, L.; Liu, J. Review of functionalization, structure and properties of graphene/polymer composite
fibers. Compos. Part A Appl. Sci. Manuf. 2016, 87, 29–45. [CrossRef]
78. Zhao, Y.; Qamar, S.A.; Qamar, M.; Bilal, M.; Iqbal, H.M. Sustainable remediation of hazardous environmental pollutants using
biochar-based nanohybrid materials. J. Environ. Manag. 2021, 300, 113762. [CrossRef]
79. Velusamy, K.; Devanand, J.; Kumar, P.S.; Soundarajan, K.; Sivasubramanian, V.; Sindhu, J.; Vo, D.-V.N. A review on nano-catalysts
and biochar-based catalysts for biofuel production. Fuel 2021, 306, 121632. [CrossRef]
Polymers 2023, 15, 3981 30 of 32

80. Rjeily, M.A.; Gennequin, C.; Pron, H.; Abi-Aad, E.; Randrianalisoa, J.H. Pyrolysis-catalytic upgrading of bio-oil and pyrolysis-
catalytic steam reforming of biogas: A review. Environ. Chem. Lett. 2021, 19, 2825–2872. [CrossRef]
81. Aminu, I.; Nahil, M.A.; Williams, P.T. Hydrogen Production by Pyrolysis–Nonthermal Plasma/Catalytic Reforming of Waste
Plastic over Different Catalyst Support Materials. Energy Fuels 2022, 36, 3788–3801. [CrossRef]
82. Zhang, Q.; Khan, M.U.; Lin, X.; Cai, H.; Lei, H. Temperature varied biochar as a reinforcing filler for high-density polyethylene
composites. Compos. Part B Eng. 2019, 175, 107151. [CrossRef]
83. Cruz, G.; Crnkovic, P.M. Effects of High Temperature in the Combustion Chamber of a Drop Tube Furnace (DTF) for Different
Thermochemical Processes. J. Energy Res. Rev. 2019, 2, 1–10. [CrossRef]
84. Bartoli, M.; Arrigo, R.; Malucelli, G.; Tagliaferro, A.; Duraccio, D. Recent Advances in Biochar Polymer Composites. Polymers
2022, 14, 2506. [CrossRef]
85. Kapoore, R.V.; Butler, T.O.; Pandhal, J.; Vaidyanathan, S. Microwave-Assisted Extraction for Microalgae: From Biofuels to
Biorefinery. Biology 2018, 7, 18. [CrossRef] [PubMed]
86. Das, O.; Bhattacharyya, D.; Hui, D.; Lau, K.-T. Mechanical and flammability characterisations of biochar/polypropylene
biocomposites. Compos. Part B Eng. 2016, 106, 120–128. [CrossRef]
87. Chen, L.; Zhang, Y.; Wang, L.; Ruan, S.; Chen, J.; Li, H.; Yang, J.; Mechtcherine, V.; Tsang, D.C. Biochar-augmented carbon-negative
concrete. Chem. Eng. J. 2021, 431, 133946. [CrossRef]
88. Ayadi, R.; Koubaa, A.; Braghiroli, F.; Migneault, S.; Wang, H.; Bradai, C. Effect of the Pyro-Gasification Temperature of Wood on
the Physical and Mechanical Properties of Biochar-Polymer Biocomposites. Materials 2020, 13, 1327. [CrossRef]
89. Bartoli, M.; Troiano, M.; Giudicianni, P.; Amato, D.; Giorcelli, M.; Solimene, R.; Tagliaferro, A. Effect of heating rate and feedstock
nature on electrical conductivity of biochar and biochar-based composites. Appl. Energy Combust. Sci. 2022, 12, 100089. [CrossRef]
90. Das, C.; Tamrakar, S.; Kiziltas, A.; Xie, X. Incorporation of Biochar to Improve Mechanical, Thermal and Electrical Properties of
Polymer Composites. Polymers 2021, 13, 2663. [CrossRef]
91. Zhu, J.; Abeykoon, C.; Karim, N. Investigation into the effects of fillers in polymer processing. Int. J. Light. Mater. Manuf. 2021, 4,
370–382. [CrossRef]
92. Praveenkumara, J.; Madhu, P.; Gowda, T.G.Y.; Sanjay, M.R.; Siengchin, S. A comprehensive review on the effect of synthetic filler
materials on fiber-reinforced hybrid polymer composites. J. Text. Inst. 2021, 113, 1231–1239. [CrossRef]
93. Chen, R.; Yu, R.; Pei, X.; Wang, W.; Li, D.; Xu, Z.; Luo, S.; Tang, Y.; Deng, H. Interface design of carbon filler/polymer composites
for electromagnetic interference shielding. New J. Chem. 2021, 45, 8370–8385. [CrossRef]
94. Kim, K.-H.; Ong, J.L.; Okuno, O. The effect of filler loading and morphology on the mechanical properties of contemporary
composites. J. Prosthet. Dent. 2002, 87, 642–649. [CrossRef]
95. Behazin, E.; Misra, M.; Mohanty, A.K. Compatibilization of toughened polypropylene/biocarbon biocomposites: A full factorial
design optimization of mechanical properties. Polym. Test. 2017, 61, 364–372. [CrossRef]
96. Ogunsona, E.O.; Misra, M.; Mohanty, A.K. Impact of interfacial adhesion on the microstructure and property variations of
biocarbons reinforced nylon 6 biocomposites. Compos. Part A Appl. Sci. Manuf. 2017, 98, 32–44. [CrossRef]
97. Ouyang, Y.; Bai, L.; Tian, H.; Li, X.; Yuan, F. Recent progress of thermal conductive ploymer composites: Al2O3 fillers, properties
and applications. Compos. Part A Appl. Sci. Manuf. 2021, 152, 106685. [CrossRef]
98. Ronsse, F.; van Hecke, S.; Dickinson, D.; Prins, W. Production and characterization of slow pyrolysis biochar: Influence of
feedstock type and pyrolysis conditions. GCB Bioenergy 2012, 5, 104–115. [CrossRef]
99. Dhahak, A.; Grimmer, C.; Neumann, A.; Rüger, C.; Sklorz, M.; Streibel, T.; Zimmermann, R.; Mauviel, G.; Burkle-Vitzthum, V.
Real time monitoring of slow pyrolysis of polyethylene terephthalate (PET) by different mass spectrometric techniques. Waste
Manag. 2020, 106, 226–239. [CrossRef] [PubMed]
100. Hu, X.; Gholizadeh, M. Biomass pyrolysis: A review of the process development and challenges from initial researches up to the
commercialisation stage. J. Energy Chem. 2019, 39, 109–143. [CrossRef]
101. Ramanathan, A.; Begum, K.M.M.S.; Pereira, A.O.; Cohen, C. Pyrolysis of waste biomass: Toward sustainable development. In A
Thermo-Economic Approach to Energy from Waste; Elsevier: Amsterdam, The Netherlands, 2022. [CrossRef]
102. Leng, L.; Xiong, Q.; Yang, L.; Li, H.; Zhou, Y.; Zhang, W.; Jiang, S.; Li, H.; Huang, H. An overview on engineering the surface area
and porosity of biochar. Sci. Total. Environ. 2020, 763, 144204. [CrossRef]
103. Xu, Z.; He, M.; Xu, X.; Cao, X.; Tsang, D.C. Impacts of different activation processes on the carbon stability of biochar for oxidation
resistance. Bioresour. Technol. 2021, 338, 125555. [CrossRef]
104. Su, B.; Cao, Z.-C.; Shi, Z.-J. Exploration of Earth-Abundant Transition Metals (Fe, Co, and Ni) as Catalysts in Unreactive Chemical
Bond Activations. Accounts Chem. Res. 2015, 48, 886–896. [CrossRef]
105. Alghyamah, A.A.; Elnour, A.Y.; Shaikh, H.; Haider, S.; Poulose, A.M.; Al-Zahrani, S.; Almasry, W.A.; Park, S.Y. Biochar/polypropylene
composites: A study on the effect of pyrolysis temperature on crystallization kinetics, crystalline structure, and thermal stability.
J. King Saud Univ. Sci. 2021, 33, 101409. [CrossRef]
106. Tomczyk, A.; Sokołowska, Z.; Boguta, P. Biochar physicochemical properties: Pyrolysis temperature and feedstock kind effects.
Rev. Environ. Sci. Bio/Technol. 2020, 19, 191–215. [CrossRef]
107. Khodaei, H.; Gonzalez, L.; Chapela, S.; Porteiro, J.; Nikrityuk, P.; Olson, C. CFD-based coupled multiphase modeling of biochar
production using a large-scale pyrolysis plant. Energy 2021, 217, 119325. [CrossRef]
108. Panchasara, H.; Ashwath, N. Effects of Pyrolysis Bio-Oils on Fuel Atomisation—A Review. Energies 2021, 14, 794. [CrossRef]
Polymers 2023, 15, 3981 31 of 32

109. Maljaee, H.; Madadi, R.; Paiva, H.; Tarelho, L.; Ferreira, V.M. Incorporation of biochar in cementitious materials: A roadmap of
biochar selection. Constr. Build. Mater. 2021, 283, 122757. [CrossRef]
110. An, X.; Yu, J.; Yu, J.; Tahmasebi, A.; Wu, Z.; Liu, X.; Yu, B. Incorporation of biochar into semi-interpenetrating polymer networks
through graft co-polymerization for the synthesis of new slow-release fertilizers. J. Clean Prod. 2020, 272, 122731. [CrossRef]
111. Minugu, O.P.; Gujjala, R.; Shakuntala, O.; Manoj, P.; Chowdary, M.S. Effect of biomass derived biochar materials on mechanical
properties of biochar epoxy composites. Proc. Inst. Mech. Eng. Part C J. Mech. Eng. Sci. 2021, 235, 5626–5638. [CrossRef]
112. Arroyo, J.; Ryan, C. Incorporation of Carbon Nanofillers Tunes Mechanical and Electrical Percolation in PHBV:PLA Blends.
Polymers 2018, 10, 1371. [CrossRef] [PubMed]
113. Das, O.; Sarmah, A.K.; Zujovic, Z.; Bhattacharyya, D. Characterisation of waste derived biochar added biocomposites: Chemical
and thermal modifications. Sci. Total. Environ. 2016, 550, 133–142. [CrossRef]
114. Yasim-Anuar, T.A.T.; Yee-Foong, L.N.; Lawal, A.A.; Farid, M.A.A.; Yusuf, M.Z.M.; Hassan, M.A.; Ariffin, H. Emerging application
of biochar as a renewable and superior filler in polymer composites. RSC Adv. 2022, 12, 13938–13949. [CrossRef]
115. Zouari, M.; Devallance, D.B.; Marrot, L. Effect of Biochar Addition on Mechanical Properties, Thermal Stability, and Water
Resistance of Hemp-Polylactic Acid (PLA) Composites. Materials 2022, 15, 2271. [CrossRef]
116. Zhang, Q.; Cai, H.; Yang, K.; Yi, W. Effect of biochar on mechanical and flame retardant properties of wood—Plastic composites.
Results Phys. 2017, 7, 2391–2395. [CrossRef]
117. Wu, S.; Chen, Y.; Chen, Z.; Wang, J.; Cai, M.; Gao, J. Shape-stabilized phase change material with highly thermal conductive
matrix developed by one-step pyrolysis method. Sci. Rep. 2021, 11, 822. [CrossRef]
118. Atinafu, D.G.; Yun, B.Y.; Yang, S.; Kim, S. Encapsulation of dodecane in gasification biochar for its prolonged thermal/shape
stability, reliability, and ambient enthalpy storage. Chem. Eng. J. 2022, 437, 135407. [CrossRef]
119. Fazli, A.; Rodrigue, D. Phase morphology, mechanical, and thermal properties of fiber-reinforced thermoplastic elastomer: Effects
of blend composition and compatibilization. J. Reinf. Plast. Compos. 2021, 41, 267–283. [CrossRef]
120. Nan, N.; DeVallance, D.B.; Xie, X.; Wang, J. The effect of bio-carbon addition on the electrical, mechanical, and thermal properties
of polyvinyl alcohol/biochar composites. J. Compos. Mater. 2015, 50, 1161–1168. [CrossRef]
121. Atta, M.; Henaish, A.; Elbasiony, A.; Taha, E.O.; Dorgham, A. Structural, optical, and thermal properties of PEO/PVP blend
reinforced biochar. Opt. Mater. 2022, 127, 112268. [CrossRef]
122. Huber, T.; Misra, M.; Mohanty, A.K. The effect of particle size on the rheological properties of polyamide 6/biochar composites.
AIP Conf. Proc. 2015, 1664, 150004. [CrossRef]
123. Abbasi, S.; Ladani, R.; Wang, C.; Mouritz, A. Boosting the electrical conductivity of polymer matrix composites using low
resistivity Z-filaments. Mater. Des. 2020, 195, 109014. [CrossRef]
124. Kumar, R.; Gunjal, J.; Chauhan, S. Effect of carbonization temperature on properties of natural fiber and charcoal filled hybrid
polymer composite. Compos. Part B Eng. 2021, 217, 108846. [CrossRef]
125. Nakayama, S.F.; Yoshikane, M.; Onoda, Y.; Nishihama, Y.; Iwai-Shimada, M.; Takagi, M.; Kobayashi, Y.; Isobe, T. Worldwide
trends in tracing poly- and perfluoroalkyl substances (PFAS) in the environment. TrAC—Trends Anal. Chem. 2019, 121, 115410.
[CrossRef]
126. Arrigo, R.; Bartoli, M.; Malucelli, G. Poly(lactic Acid)–Biochar Biocomposites: Effect of Processing and Filler Content on
Rheological, Thermal, and Mechanical Properties. Polymers 2020, 12, 892. [CrossRef] [PubMed]
127. Das, O.; Sarmah, A.K.; Bhattacharyya, D. A novel approach in organic waste utilization through biochar addition in
wood/polypropylene composites. Waste Manag. 2015, 38, 132–140. [CrossRef] [PubMed]
128. Pudełko, A.; Postawa, P.; Stachowiak, T.; Malińska, K.; Dróżdż, D. Waste derived biochar as an alternative filler in biocomposites—
Mechanical, thermal and morphological properties of biochar added biocomposites. J. Clean. Prod. 2020, 278, 123850. [CrossRef]
129. Sundarakannan, R.; Arumugaprabu, V.; Manikandan, V.; Vigneshwaran, S. Mechanical property analysis of biochar derived from
cashew nut shell waste reinforced polymer matrix. Mater. Res. Express 2019, 6, 125349. [CrossRef]
130. Zhang, Q.; Zhang, D.; Xu, H.; Lu, W.; Ren, X.; Cai, H.; Lei, H.; Huo, E.; Zhao, Y.; Qian, M.; et al. Biochar filled high-density
polyethylene composites with excellent properties: Towards maximizing the utilization of agricultural wastes. Ind. Crop. Prod.
2020, 146, 112185. [CrossRef]
131. Huang, C.-C.; Chang, C.-W.; Jahan, K.; Wu, T.-M.; Shih, Y.-F. Effects of the Grapevine Biochar on the Properties of PLA Composites.
Materials 2023, 16, 816. [CrossRef] [PubMed]
132. Zhang, Q.; Li, K.; Fang, Y.; Guo, Z.; Wei, Y.; Sheng, K. Conversion from bamboo waste derived biochar to cleaner composites:
Synergistic effects of aramid fiber and silica. J. Clean Prod. 2022, 347, 131336. [CrossRef]
133. Dahal, R.K.; Acharya, B.; Saha, G.; Bissessur, R.; Dutta, A.; Farooque, A. Biochar as a filler in glassfiber reinforced composites:
Experimental study of thermal and mechanical properties. Compos. Part B Eng. 2019, 175, 107169. [CrossRef]
134. Das, O.; Kim, N.K.; Sarmah, A.K.; Bhattacharyya, D. Development of waste based biochar/wool hybrid biocomposites: Flamma-
bility characteristics and mechanical properties. J. Clean. Prod. 2017, 144, 79–89. [CrossRef]
135. Giorcelli, M.; Khan, A.; Pugno, N.M.; Rosso, C.; Tagliaferro, A. Biochar as a cheap and environmental friendly filler able to
improve polymer mechanical properties. Biomass Bioenergy 2018, 120, 219–223. [CrossRef]
136. Jayabalakrishnan, D.; Prabhu, P.; Iqbal, S.M.; Mugendiran, V.; Ravi, S.; Prakash, V.R.A. Mechanical; dielectric, and hydrophobicity
behavior of coconut shell biochar toughened Caryota urens natural fiber reinforced epoxy composite. Polym. Compos. 2022, 43,
493–502. [CrossRef]
Polymers 2023, 15, 3981 32 of 32

137. Nam, N.H.; Anh, K.D.; Truc, L.G.T.; Ha, T.A.; Ha, V.T.T. Pyrolysis of cashew nut shell: A parametric study. Vietnam. J. Chem. 2020,
58, 506–511.
138. Matta, S.; Bartoli, M.; Frache, A.; Malucelli, G. Investigation of Different Types of Biochar on the Thermal Stability and Fire
Retardance of Ethylene-Vinyl Acetate Copolymers. Polymers 2021, 13, 1256. [CrossRef] [PubMed]
139. Paul, D.; Robeson, L. Polymer nanotechnology: Nanocomposites. Polymer 2008, 49, 3187–3204. [CrossRef]
140. Kasgoz, A.; Akın, D.; Ayten, A.I.; Durmus, A. Effect of different types of carbon fillers on mechanical and rheological properties
of cyclic olefin copolymer (COC) composites. Compos B Eng. 2014, 66, 126–135. [CrossRef]
141. Lee, J.H.; Jang, Y.K.; Hong, C.E.; Kim, N.H.; Li, P.; Lee, H.K. Effect of carbon fillers on properties of polymer composite bipolar
plates of fuel cells. J. Power Sources 2009, 193, 523–529. [CrossRef]
142. Ray, J.R.; Shabtai, I.A.; Teixidó, M.; Mishael, Y.G.; Sedlak, D.L. Polymer-clay composite geomedia for sorptive removal of trace
organic compounds and metals in urban stormwater. Water Res. 2019, 157, 454–462. [CrossRef]
143. Korey, M.; Rencheck, M.L.; Tekinalp, H.; Wasti, S.; Wang, P.; Bhagia, S.; Walker, R.; Smith, T.; Zhao, X.; Lamm, M.E.; et al. Recycling
polymer composite granulate/regrind using big area additive manufacturing. Compos. B Eng. 2023, 256, 110652. [CrossRef]
144. Antunes, P.; Ramalho, A.; Carrilho, E. Mechanical and wear behaviours of nano and microfilled polymeric composite: Effect of
filler fraction and size. Mater. Des. 2014, 61, 50–60. [CrossRef]
145. Hardinnawirda, K.; Aisha, I.S. Effect of Rice Husks as Filler in Polymer Matrix Composites. J. Mech. Eng. Sci. 2012, 2, 181–186.
[CrossRef]
146. Sudheer, M.; Prabhu, R.; Raju, K.; Bhat, T. Effect of Filler Content on the Performance of Epoxy/PTW Composites. Adv. Mater. Sci.
Eng. 2014, 2014, 970468. [CrossRef]
147. Guermazi, N.; Haddar, N.; Elleuch, K.; Ayedi, H.F. Effect of filler addition and weathering conditions on the performance of
PVC/CaCO3composites. Polym. Compos. 2015, 37, 2171–2183. [CrossRef]
148. Huang, H.-X.; Zhang, J.-J. Effects of filler-filler and polymer-filler interactions on rheological and mechanical properties of
HDPE-wood composites. J. Appl. Polym. Sci. 2009, 111, 2806–2812. [CrossRef]
149. Gupta, N.; Brar, B.S.; Woldesenbet, E. Effect of filler addition on the compressive and impact properties of glass fibre reinforced
epoxy. Bull. Mater. Sci. 2001, 24, 219–223. [CrossRef]
150. Munde, Y.S.; Ingle, R.B.; Siva, I. Effect of sisal fiber loading on mechanical, morphological and thermal properties of extruded
polypropylene composites. Mater. Res. Express 2019, 6, 085307. [CrossRef]
151. Yang, L.; Han, P.; Gu, Z. Grafting of a novel hyperbranched polymer onto carbon fiber for interfacial enhancement of carbon fiber
reinforced epoxy composites. Mater. Des. 2021, 200, 109456. [CrossRef]
152. Cappello, M.; Rossi, D.; Filippi, S.; Cinelli, P.; Seggiani, M. Wood Residue-Derived Biochar as a Low-Cost, Lubricating Filler in
Poly(butylene succinate-co-adipate) Biocomposites. Materials 2023, 16, 570. [CrossRef] [PubMed]
153. Awad, S. Swelling, Thermal and Mechanical Characterizations of High-Density Polyethylene/ Recycled Biochar Composites. J.
Turk. Chem. Soc. Sect. A Chem. 2021, 8, 1137–1144. [CrossRef]
154. Giorcelli, M.; Savi, P.; Khan, A.; Padovano, E.; Tagliaferro, A. Thermal treatments for biochar and their electrical characterization
in epoxy resin composites. AIP Conf. Proc. 2018, 1981, 020022. [CrossRef]
155. Wystalska, K.; Kwarciak-Kozłowska, A. The Effect of Biodegradable Waste Pyrolysis Temperatures on Selected Biochar Properties.
Materials 2021, 14, 1644. [CrossRef]
156. Akpasi, S.O.; Anekwe, I.M.S.; Adedeji, J.; Kiambi, S.L.; Akpasi, S.O.; Anekwe, I.M.S.; Adedeji, J.; Kiambi, S.L. Biochar Development
as a Catalyst and Its Application, Biochar—Productive Technologies, Properties and Applications; IntechOpen: London, UK, 2022.
[CrossRef]
157. Ibrahim, I.; Tsubota, T.; Hassan, M.A.; Andou, Y. Surface Functionalization of Biochar from Oil Palm Empty Fruit Bunch through
Hydrothermal Process. Processes 2021, 9, 149. [CrossRef]
158. Jeffery, S.; Meinders, M.B.J.; Stoof, C.; Bezemer, T.M.; Voorde, T.F.J.V.; Mommer, L.; Van Groenigen, J.W.; Jeffery, S.; Meinders,
M.B.J.; Stoof, C.; et al. Why biochar application did not improve the soil water retention of a sandy soil: An investigation into the
underlying mechanisms. EGUGA 2015, 17, 10226.
159. Huang, Y.; Anderson, M.; Lyons, G.; McRoberts, W.; Wang, Y.; McIlveen-Wright, D.; Roskilly, A.; Hewitt, N. Techno-economic
Analysis of BioChar Production and Energy Generation from Poultry Litter Waste. Energy Procedia 2014, 61, 714–717. [CrossRef]
160. Xiao, L.; Feng, L.; Yuan, G.; Wei, J. Low-cost field production of biochars and their properties. Environ. Geochem. Heal. 2019, 42,
1569–1578. [CrossRef]

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