Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Contents lists available at ScienceDirect

Advanced Industrial and Engineering Polymer Research

journal homepage: http://www.keaipublishing.com/aiepr

Engineering flame and mechanical properties of natural plant-based

fibre biocomposites
Mojtaba Ahmadi a, Omid Zabihi a, Zahra Komeily Nia a, Vishnu Unnikrishnan a,
Colin J. Barrow b, Minoo Naebe a, b, *
a
Institute for Frontier Materials (IFM), Deakin University, Waurn Ponds, VIC, 3216, Australia
b
Centre for Sustainable Bioproducts, Deakin University, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The escalating global concerns surrounding unsustainable petroleum consumption have fueled interest
Received 13 December 2023 in natural plant fiber polymer biocomposites (NFPCs) as eco-friendly alternatives. NFPCs offer advantages
Received in revised form such as low density, specific mechanical properties, recyclability, and biodegradability. Despite their
24 June 2024
potential for addressing environmental issues and serving as cost-effective alternatives for per- and
Accepted 22 August 2024
polyfluoroalkyl substances (PFAS) remediation, challenges exist due to their poor thermal stability and
flammability. This comprehensive review delves into efforts to enhance the flame resistance of NFPCs,
Keywords:
focusing on flammability testing methods, the impact of flame retardants, and underlying flammability
Fire retardancy
Natural fibre
mechanisms. Emphasizing the delicate balance between flame resistance and structural integrity, the
Biocomposites review establishes a framework for understanding the thermo-structural response of burning NFPCs.
Sustainability Additionally, it explores sustainability and recycling aspects, offering insights crucial for comprehending
fire-induced damage processes in NFPCs, especially in high-performance applications where exposure to
high temperatures is inevitable.
© 2024 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi
Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction fibre-reinforced bio-based polymers, “green composites”, which

can offer an environmentally friendly replacement to conventional
The origin of composites can be traced back to 3400 BCE when materials. The definition of biocomposites has been extended to
early Mesopotamian settlers and Egyptians began using natural- include other combinations, such as natural fibre-reinforced pe-
based materials, such as wood strips, combined with glue. troleum-derived polymers and synthetic fibre-reinforced bio-
Approximately 3000 years ago, houses were constructed using polymers [4,5]. These natural fibres can be derived from animals,
straw as natural reinforcement materials mixed with clay [1]. After minerals, and plants. Animal fibres such as hair and silk are rarely
the Industrial Revolution, the umbrella term “biocomposites” used in biocomposite fabrication. Mineral fibres such as asbestos
began to capture the attention of industrialists like Henry Ford. are carcinogenic and non-renewable. However, plant fibres are
Inspired by the remarkable idea of using natural materials with renewable and biodegradable, with lower density than synthetic
strength comparable to chicken bones, he pioneered the fabrication fibre and high specific tensile properties (e.g., stiffness and
of the prototype car based on hemp fibre in the early 1940s [2]. strengths). Therefore, it exhibits significant lightweight, low-cost,
During the Second World War, the flax yarn impregnated with and improved surface finish of composite moulded parts. More-
phenolic resin was used in the fuselage of de Havilland DH.88 over, natural fibres are abundant renewable resources that exhibit
Comet [3]. Therefore, it can be concluded that the origination of enhanced mechanical behaviour and are biodegradable [6,7].
composite started with biocomposite fabrication. Biocomposites Compared to fibres derived from mineral and animal, plant-based
and or natural fibre polymer composites (NFPC) consist of natural fibres have shown higher renewability and Sustainability, lower
* Corresponding author. Institute for Frontier Materials (IFM), Deakin University, environmental impact during processing stage, reduction of weight
Waurn Ponds, VIC, 3216, Australia. of finished products, cost-effectiveness, easier biodegradability and
E-mail address: [email protected] (M. Naebe). recyclability. Additionally, their surface chemistry can easily be
Peer review under the responsibility of Kingfa Scientific and Technological Co.,
modified for application in polymeric composites [8,9].
Ltd.

https://doi.org/10.1016/j.aiepr.2024.08.002
2542-5048/© 2024 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article as: M. Ahmadi, O. Zabihi, Z.K. Nia et al., Engineering flame and mechanical properties of natural plant-based fibre
biocomposites, Advanced Industrial and Engineering Polymer Research, https://doi.org/10.1016/j.aiepr.2024.08.002
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

The use of natural fibres in polymeric matrices including ther- concerns. It is often understood that all polymeric materials and
mosets and thermoplastics can affect mechanical, thermal, and natural fibres inherently burn swiftly once exposed to fire, pri-
flammability behaviour [8]. Cellulose, hemicellulose, and lignin are marily due to the presence of hydrocarbon chains and, specif-
inherently combustible and can facilitate the ignitability and fire ically, hemicellulose and cellulose. Furthermore, although the
propagation in NFPCs composites, whereas bamboo and flax can manipulation of composites through the use of flame retardants
equip the composite with some inherent flame-retardant charac- can outrun the flammability of NFPCs and reduce the candlewick
teristics due to their silica content and insulating porous structures. effect [6,7,15], the loss of structural integrity and mechanical
Furthermore, the interface also has its own role while dealing with performance can cause massive damage to property and severe
flammability of NFPCs. For example, the formations of air pockets at risks to human [15].
the interfacial zone can acts as feed for combustion zone and As illustrated in Fig. 2, Fire retardants have been utilised for
facilitate the fire spread. Therefore, tailoring the inherent proper- natural fibre for quite a long time. The history of flame retardancy in
ties of natural fibres and their interfacial interactions can become natural fibres and natural-based materials such as wood can be
an active area of research to understand the combustion properties traced back to when the reconstruction was carried out after the
of NFPCs better-hence developing flame retardant sustainable Great Fire of Rome. Emperor Nero ordered wood to be soaked in salt
composites [10,11]. water before use. In 1638, canvas used in Persian theatres was
As seen in Fig. 1aea wide variety of natural fibres have been treated to improve fire retardancy. Following that, in 1783, the
introduced, each making different contributions to the fabrication Montgolfier brothers coated a lighter-than-air balloon with alum.
of NFPC. Among them, hemp fibre, known as “a miracle plant”, is During the 18th-19th century, Gay-Lussac and William Henry Per-
popular since it is the most sustainable material. In other words, it kin made further progress by running different experiments with
is a crop that generates zero waste, positively impacts carbon inorganic salt. Their investigation led to an understanding of the
emissions, and yields a high output [12]. Although natural fibres fire retardancy mechanisms of inorganic salt. During World War II,
were used for non-structural applications, recent developments in there was a focus on fire retardants for wooden products and tex-
improving the fibre-matrix performance for structural applications tiles for military applications [16,17]. Special attention has been
have made significant breakthroughs in utilizing natural fibres for paid to the cellulosic fabric among different natural materials. A
automotive, sports goods and construction industries [13]. In vast range of flame retardants, including simple salts ammonium
accordance with the needs of various sectors, the harvested fibres chloride [18], diammonium phosphate [19], sodium silicate [20],
can undergo multiple stages, including selection/modifications, boric acid [21], aluminium hydroxide, zinc borate [22], chlorides of
processing, assembly, and production, to create biodegradable calcium, tin, and calcium sulphate have been investigated [23]. At
products that possess distinct properties, Fig. 1b [14]. As NFPC the beginning of the 20th century, the distinguished dye chemist
continues gaining prominence across various engineering disci- William Henry Perkin focused on the requirements for a flame-
plines, industries including Ford, Audi, Opel, Daimler, and Mercedes proofing process on cotton fabrics. The flame-proofing process
have recognised their significant importance. More interestingly, necessitates careful consideration of the cloth's durability to ensure
the advancements in the NFPCs have identified novel applications it remains undamaged throughout the treatment. Building upon
in sports, aerospace, etc. This has led to heightened motivation the findings of Perkin and various other researchers, a commercial
among researchers, resulting in a continuous increase in publica- process known as “non-flame” was initiated. Their efforts have
tions on the subject Fig. 1c [7]. evolved into foundational observations and outcomes that remain
Even meeting the stringent standards required for many relevant and applicable today [24]. In today's context, when
public transportation and infrastructure applications has pre- considering the expectations for ideal fire-retardant materials,
sented a challenge. Their susceptibility to heat and fire and poor several properties should be considered. These requirements are
flame-retardant resistance have raised significant safety focused on achieving a high level of fire protection effectiveness,

Fig. 1. (a) Various natural fibres used for NFPCs fabrication, (b) NFPCs fabrication protocol and properties, and (c) number of publications in “natural fibres/fibres” and “natural
fibres/fibres polymer composites” topics over the two last decades.

2
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 2. History of flame-retardant application in natural fibres/fabric.

ensuring good chemical stability of flame retardant, minimising 2. Flammability/fire specifications

impact on mechanical properties, maintaining insecticidal effec-
tiveness, cost-effectiveness, water resistance, absence of toxic gas 2.1. Flammability/fire terms
emissions, and ease of application [25]. Considering these multiple
requirements, generally, a combination of flame retardants is used Regarding the flammability of composites, having a clear un-
to fulfil criteria defined in design standards. derstanding of the stages in the fire development scenario, as
Accordingly, understanding the mechanisms and the correlation illustrated in Fig. 3, can serve as a crucial foundation for effective fire
between flammability and mechanical performance of NFPCs can and flame management strategies. At each stage, various fire and
provide valuable insights for various sectors, including consumer flammability tests for composites can typically be conducted to
electronics, Federal Aviation Regulations and National Building simulate and forecast the fire resistance of NFPCs. Additionally, as
Codes. This understanding allows for developing a well-balanced time progresses, factors such as the extent of flame propagation
strategy that aligns thermo-mechanical properties with flamma- from the ignition source (flame spread) and the composites'
bility test criteria and national standard requirements. This review contribution to the fire when exposed to flames (reaction to fire) can
paper will begin by discussing various flammability testing pro- significantly influence the duration of the fire and its subsequent
tocols, standards, and approaches in the first section. The second decay stage. In this regard, various terms are defined to assess the
and third sections will explore the thermal decomposition and combustion characteristics of composites during fire development
thermal behaviour of natural fibre and NFPCs. In the fourth section, [26]. First, ignition, the initiation of combustion, occurs under heat
we will elaborate on the most recent techniques designed to flux and oxygen environment. The ignition time (Tig) indicates how
enhance the flame resistance of NFPCs, highlighting their effects on quickly the composite's surface reaches the pyrolysis temperature
the mechanical performance of these composites. and its ability to generate a critical amount of flammable volatile
This review paper is organized to provide a comprehensive gases during combustion [27]. Once the combustion starts, the heat
understanding of the fire-related properties and safety consider- begins to be released into the environment. Temperature exceeding
ations for NFPCs. The introduction section starts by discussing the 350e500
C during fire growth will help fire propagation. During the
importance of flammability and fire requirements for composite fire propagation, the volatile and heat are continuously released into
materials. The following sections then explore the specific details the environment. The heat release rate (HRR) indicates the extent of
of flammability; the second section covers the key terms and thermal energy released per unit surface area upon exposure to a fire
relevant test methods used to assess the fire performance of ma- or external heat flux, which correlates with the oxygen consumption
terials. Subsequently, the third section of this review paper focuses rate. Once the fire temperature exceeds 600
C, the fire is fueled by all
on the fire-related characteristics of natural fibres themselves. It gas-phase combustible items. The flashover occurs at this step, and
looks at the factors that affect their ability to burn, the underlying the heat release rate reaches the fastest level, known as the peak
mechanisms of their fire behaviour, and techniques to improve value of HRR (PHRR). This quantity also measures a material's
their natural fire resistance. Building on this, the fourth section maximum flammability potential [28]. The temperature can reach
deals with the fire performance of NFPCs. It explores the factors higher values, i.e., 900e1000
C, and the fully developed fire is
affecting their overall fire behaviour, the complex fire mechanisms accompanied by dark and black smoke [29]. The decay stages start
involved, and strategies to improve the fire safety of these com- after all the fuels, including gas and condensed phases, are
posites using fire-resistant additives and treatments. The fifth consumed by fire. During the combustion, from the initial stage to
section then addresses the sustainability and recycling aspects of the decay stage, the heat is released, and the total heat release (THR),
NFPCs, recognizing the need for environmentally-friendly and the area under the heat release rates-burning time plot, defines the
resource-efficient composite materials. Finally, the conclusion total released thermal energy of a material during its complete
summarizes the key insights and findings presented throughout combustion in air-oxygen [30]. All organic materials, such as
the review paper. natural-based materials and synthetic compounds, experience mass

3
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 3. Modern fibre development in natural fibre composites.

loss during pyrolysis, which coincides with char formation. considered different qualitative indicators for pass/fail criteria.
Depending on the fire resistance level and severity of the flame, However, concerning the fire tests, a more accurate experimental
materials show different mass loss rates (MLR). This parameter test is designed, and this can convey a comprehensive study of
controls the HRR and THR values [31]. Char yield refers to the dif- polymer fire behaviour and their combustion mechanisms. These
ference in the mass of a specimen before and after pyrolysis. Indeed, tests can represent real-life scenarios according to different heat
a high char yield indicates that a more significant amount of carbon flux through separate heat transferring means, including conduc-
or inorganic material has remained due to pyrolysis [32,33]. The tion, convection, and radiation in hot spark and flame. Compared to
amorphous char can be formed by using ingredients of materials or the fire tests, passing the flammability tests is dealing with lower
external carbon generators such as intumescent flame retardants performance of materials. In other words, sometimes, despite
[34]. According to this scenario, various terms such as HRR, THR, passing the flammability test, the materials are still hazardous
MLR, smoke density, char residue, flameout time and ignition time when involved in fire. Therefore, there will be a need for measuring
are the critical parameters for investigating fire properties in fire-test-response characteristics through fire tests [36e38]. The
biocomposites. number of flammability and fire tests is not limited to hundreds of
polymers and polymer-based composite tests. But, among them,
2.2. Flammability/fire tests and standards experimentalists have incorporated a few critical tests widely. Their
results and observations are essential for designing and fabricating
Although there is little difference between the fire and flam- products for a fire-safe environment. Concerning flammability
mability tests, a common aim of both flammability and fire tests is tests, UL-94 is one of the most known bench-scale test methods,
to obtain data for regulatory compliance, quality assurance/ which can be conducted through two horizontal burning methods
research, and data for fire safety engineering design/analysis [35]. or three vertical burning test methods. However, regarding the fire
In this regard, regulation and safety codes are generally based on tests, their test procedures and setups are more complicated and
two schemes. The first scheme deals with preventing and mini- require pre-conditioning environmental controls because these
mising the possibility of ignition, whereas the second strategy fo- tests deal with samples designed for unique applications. In other
cuses on managing the impact of fire. The flammability and fire words, the Steiner tunnel test, the radiant flooring panel tests, and
tests are associated with the first and second strategies. In other the rate of heat release test for aircraft cabin materials have been
words, in flammability tests, a small heat source, i.e., direct expo- used for the investigation of wind-aided flame spread propensity of
sure to flame, is used to expose NFPCs or polymers to a small heat the wood-based building material, the fire hazard of floor coverings
source for a specified short period. During the experiment, the (e.g., biocomposites), and fire behaviour of aviation cabin including
ignition of material, formation of flaming or non-flaming droplets, natural phase component, respectively [39e41]. In addition to
and the level of smouldering after removal of fibre can be these tests, several testing techniques are used for research and
4
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

quality assurance. These tests can be classified into bench-scale and environmental, external, and internal factors can affect the extent
large-scale test methods. This classification is built on the flame of its ignition time and its thermal stability, as illustrated in Fig. 5.
tests' purpose, the fire scale (varies from ~0.001 to 36 m2) and the These factors can be related to the size and dimensions of samples,
application of the composite [42]. ignition source, environmental pressure/temperature, and humid-
The UL-94 test is known as a widely utilised and standardized ity. Additionally, the available oxygen and air flow are other
technique for qualitatively investigating the flammability of poly- external factors affecting natural fibres' flammability duration [54].
mers (virgin polymers and composites), providing cost-effective Compared to the external factors, internal factors can affect the
way to classify their fire/combustion behaviour. But it suffers from mechanical and flammability of the natural fibres. The internal
some limitations. For example, the UL-94 test has been criticized for factors are chemical composite, structural properties, and fibre
not accurately predicting real-world fire behaviour, as it only deals morphology. Also, the inherited mechanical, thermal, and physical
with evaluation of ignition and initial flame spread, rather than in- properties of natural fibre can be affected by the cultivation con-
depth fire behaviour [43,44]. On the other hand, the Cone Calo- ditions, such as the maturity of the plant fibre, harvesting season,
rimeter method provides a more comprehensive assessment of fire and soil/weather conditions [55]. For example, Jute fibre harvested
behaviour by measuring key combustion parameters at different at 105 days has the highest thermal stability and lignin content
stages of combustion including heat release rate, smoke production, [56]. The formation of cellular structure in natural fibre exhibits
and ignitability, under controlled testing preconditions. Therefore, better thermal properties due to changes in the crystallinity and
it can be concluded that it offers a more realistic evaluation of how crystallite size. In contrast, the amorphous hemicellulose can pro-
polymers will behave in actual fire scenarios compared to the vide a suitable platform on the fibre surface for chemical modifi-
limited capabilities of the UL-94 technique. Nonetheless, it has cation to improve interfacial adhesion, hence higher mechanical
some limitations such as the need for larger samples with specific properties and thermal stability of the fibre with composite prep-
dimensions, more complex testing setup and time-consuming as aration [57]. In addition to these factors, other factors, such as pre-
well as costly setup [45]. In contrast, the LOI test is a straightforward treatment, can affect the final properties of the natural fibres.
and cost-effective method for assessing the minimum oxygen level Techniques such as mercerisation, scouring, bleaching, retting,
required for polymer combustion, but it cannot directly measure degumming, stripping, mechanical decortication, chemical process,
fire behaviour under real-world scenario [46]. Similar to Cone and the like are a few examples in this regard. These techniques can
Calorimeter, PCFC test provides detailed information about the change the composition of fibre consisting of cellulose, hemicel-
thermal decomposition and combustion behaviour at molecular lulose, lignin, wax, fat, and mineral salts. In other words, the pre-
level but requires a smaller sample size; therefore, it cannot reflect treated natural plant-based fibres mainly comprise cellulose [58].
the bulk behaviour in larger-scale fire scenarios [47]. The cellulose fibre will yield char and different volatile gases during
Flammability and fire tests, as illustrated in Fig. 4, obey stan- decomposition, which can further release small carbon fragments.
dardized experimental protocols to assure reproducibility and However, the impurities in the raw fibre, such as metal salts, can act
repeatability of the results. These standards can be defined by as Lewis's acids and enhance char formation. Similarly, the higher
consensus-based committees such as ASTM International, the Na- lignin content can promote char formation since lignin is a poly-
tional Fire Protection Association, the International Organization phenolic amorphous material [32].
for Standardization, the International Electrotechnical Committee, The chemical composition of natural fibre determines the me-
and technical committees [48e50]. Concerning NFPCs, ASTM chanical properties and governs the flammability mechanisms in
D3814 has been widely used as a standard guide for locating fibres. Plant fibres have different components, such as cellulose,
combustion test methods for polymers since the reinforcing phase hemicellulose, lignin, pectin, inorganic substances, and waxes
(bio-phase) combustion behaviour is not far from polymer mate- (ash). The main constituents of lignocellulosic fibres are cellulose,
rials [51]. Furthermore, when NFPCs are used in high-performance hemicellulose, and lignin. Their content is different from plant to
applications such as aerospace and automotive, fire and or flam- plant. Table 1 displays the chemical composition and mechanical
mability tests should be carried out, and the results should meet properties of some widely used plant fibres. Considering the
the requirements defined by transport regulators. For example, amount of (%) the composition, cellulose is the main component of
Code of Federal Regulation (CFR) 25.853 for aircraft interior [52] most plant fibres and significantly impacts the flammability and
and Federal Motor Vehicle Safety Standard (FMVSS) No. 302 (49 mechanical properties of the fibres. Lignin is the second important
CFR 571.302) [53] have been dealing with different fire/flamma- constituent of plant fibre, and its aromatic rings control the
bility performance of products through investigation of results oxidation of fibres by forming insulating char and producing fewer
obtained by horizontal/vertical burning rate, smoke density, and volatiles. Char formation during lignin combustion is much greater
heat release amount/rate. than cellulose or hemicellulose. Contrary to this, cellulose makes
The UL 94 Standard, ISO 5660e1, ASTM D2863, and ASTM volatile flammables and propagates fire development [59]. Hemi-
D7309/ISO 19700 are the most common standards governing the cellulose absorbs moisture and, compared to cellulose, produces
UL-94, Cone Calorimeter test, LOI test, and PCFC techniques. more incombustible gases and less tar [59,60]. Therefore, based on
Materials are subjected to different flammability/fire tests for the chemical constituents of some plant fibres provided in Table 1,
either screening during fabrication or testing their properties. coir, with low cellulose (36e43%) and high lignin (41e45%) content,
These techniques have been used for other applications to evaluate typically has a lower flame resistance than cotton with very high
the potential of flame retardants or any chemical treatment/ cellulose (85e90%) content.
modification that has been not limited to NFPC but also any bio- In addition to the chemical compositions, plant fibres have a
composites whose components are natural-based materials. multilayer structure, Fig. 6, in which the primary wall surrounds a
secondary wall comprising three layers (S1, S2, and S3). The
3. Flammability behaviour of natural fibres thickest layer, the middle layer (S2, nearly 80% of fibre thickness),
dominates the fibre's mechanical properties. All layers are made of
3.1. Parameters affecting the flammability of natural fibres cellulose microfibrils helically twisted and bound together via
amorphous lignin (as binder). Typically, the main component of the
The thermal decomposition starts when natural fibres are plant fibres is cellulose, which is highly crystalline (with around
exposed to fire or high radiation sources. In this regard, 80% crystalline region) and is responsible for its strength.
5
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 4. The most common tests and standards used for investigation of flame/fire properties of NFPCs.

Meanwhile, hemicellulose also helps to enhance the strength of the the most critical parameters deploying the plant fibre's strength are
cell wall by forming non-covalent bonds with cellulose and lignin the crystalline region size, the microfibrils angle, the polymerisa-
[64]. Generally, a higher ignition temperature is required to tion degree, permeability, and the lumen size.
decompose a fibre with a higher crystalline structure, fibrillar Based on the information provided, it can be concluded that
orientation and degree of polymerisation. These parameters con- natural fibres’ thermal decomposition and flammability are influ-
trol the permeability of the fibre to oxygen and consequently affect enced by a range of environmental, external, and internal factors.
the fibre's flammability property. Thus, the crystalline cotton acti- Factors like size, ignition source, pressure, temperature, humidity,
vation energy is much higher than amorphous celluloses [13,59]. and air flow externally affect ignition time and thermal stability,
The lower fibre orientation and fibre aspect ratio of plant fibres while the chemical composition, structural properties, and fibre
compared to synthetic fibres is also the main reason for their poor morphology internally play a significant role. The proportions of
mechanical property [65]. In the crust of the cell wall, there is a cellulose, hemicellulose, and lignin in the fibres are particularly
hollow structure called a lumen, which transports nutrients and critical as they impact the thermal decomposition mechanisms and
moisture through capillary action, affects the absorption and char formation. For instance, highly crystalline cellulose fibres like
preservation of internal moisture and correspondingly affects the cotton demonstrate greater thermal stability compared to more
mechanical property and the fire behaviour of fibres [66]. In brief, amorphous fibres like coir. Additionally, the multilayered,
6
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 5. The effect of different factors on the flammability level of natural fibres.

microfibrillar structure of plant fibres and parameters like degree of combustion temperature of plant fibres is lower than their glass
polymerisation and lumen size also play a role in influencing their transition temperature, they form char due to having lignin in their
mechanical and flammability characteristics. Furthermore, pre- structure, which slightly improves their flammability [13]. The
treatment techniques that modify fibre composition can also alter combustion of cellulose itself, as the main constituent of the plant
thermal and fire-related properties. Understanding these intricate fibres, involves five stages: (I) water desorption, (II) formation of
relationships between the various factors is vital for the develop- dehydrocellulose upon water evolution and cross-linking of cellu-
ment of natural fibre-based materials with enhanced fire resistance lose (III) dehydrocellulose decomposition and formation of volatiles
and performance. and char (IV) levoglucosan formation, and (V) levoglucosan
decomposition and formation of combustible and incombustible
3.2. Flammability mechanisms in natural fibre gases, tar and char [8]. Lignin and hemicellulose decompose at
140e400
C and 200e260
C, respectively. The broad decomposition
Combustion is a self-driven redox process that quickly develops temperature of the lignin is because of both strong bonds (i.e., in
while releasing heat, light, and flame formation. Free radicals such as aromatic rings) and weak bonds requiring lower breakage energy
hydroxyl radicals (OH_) initiate and propagate the chain reaction of a [69]. Among the three major components, lignin was more resistant
combustion process [67]. However, combustion only happens when to decomposition. It decomposed slowly, with a meager mass loss
a chemical, physical, or microbiological stimulus interacts with air, rate over a wide temperature range from 100 to 900
C, leaving a
which further accompanies heat release. The heat source power, the solid residue. These three components show different thermal
amount of oxygen and the ease of gas transport in the area detect behaviour, possibly due to variations in their chemical and structural
how long it will take for the ignition to form [68]. Although the characteristics [70]. This mechanism is illustrated in Fig. 7.
7
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Table 1
Chemical composition and mechanical properties are common natural fibres [9,61e63].

Fibre Chemical Composition of fibre Mechanical property of fibre

Name Cellulose (%) Lignin (%) Hemicellulose (%) Ash (%) Tensile Strength (MPa) Elastic Modulus (GPa) Elongation at Break (%)

Flax 64e71 2e5 18.5e20.6 5 345e1830 27e80 1.2e3.2

Kenaf 44e57 15e19 22e23 2e5 427e519 23.1e27.1 2.2
Jute 61e72 12e13 13.6e16.7 0.5e2 393e800 10e55 1.5e1.8
Hemp 70.2e77 3.7e5.7 17.9e22.4 0.8 550e1110 58e70 1.6
Ramie 68.6e76.2 0.6e0.7 13.1e16.7 1.7 400e938 44e128 2.0e3.8
Abacca 56e63 7e10 15e17 3 418e486 12e13.8 2.9
Sisal 67.5e78 8e11 10e24 0.6e1 507e855 9.4e28 2.0e2.5
Cabuya 68e77 13 4e8 1.5e2 43e571 8.2e9.1 9.8
Cotton 85e90 7e16 1e3 0.8e2 287e800 5.5e13 3.0e10
Coir 36e43 41e45 0.15e0.25 2 131e220 4e6 15e30
Rice 28e43 12e16 23e28 15e20 450 1.2 e
Wheat 29e51 16e21 26e32 4.5e9 275 4.5e6.5 e
Barley 31e45 14e15 24e29 5e7 e 0.3e0.6 e
Oat 31e48 16e19 27e38 6e8 e e e
Rye 33e50 16e19 27e30 2e5 e e e
Bagasse 32e48 19e24 27e32 5e15 290 11 e
Bamboo 26e43 21e31 15e26 5e17 503 35.91 1.40
Esparto 33e38 17e19 27e32 6e8 18-28 (cN/tex) e e
Sabai 45 22 24 6 76 e e

Fig. 6. Structure of natural fibre.

During the thermal degradation of various types of biomass lignin, cellulose, and hemicellulose can be investigated by kinetic
samples, there is a possibility of interactions among different studies. The outcome of such studies showed a close correlation
components such as lignin, cellulose, and hemicellulose products between the activation energy and cellulose, whereas the reaction
[71]. This phenomenon varies for other plant fibres, resulting in order is more controlled by hemicellulose. Lignin with its border
different thermal degradation behaviour, as seen in Table 2. degradation range plays a vital role in the tail of TGA graphs (e.g.,
Furthermore, kinetic studies such as calculating activation en- char formation) obeying diffusion mechanisms. However, both
ergy and modelling via pyrolysis-assisted degradation can also lead autocatalysis mechanisms are more dominated by cellulose and
to understanding materials' decomposition reactions and thermal hemicellulose [71].
behaviour [73]. Different kinetic modelling such as the Kissinger,
Friedman, modified CoatseRedfern, and FlynneWalleOzawa 3.3. Fire retardancy techniques in natural fibres
methods can be used for most natural fibres. According to the
conversion rates and mass loss, most natural fibres such as bamboo, To enhance the fire resistance of lignocellulosic fibres, flame
agricultural residue, wood, and basalt fibres have shown main retardant chemicals or materials are introduced and applied to
thermal degradation at 60%, with a mass loss between 215
C and them. These flame retardants reduce the combustion rate and
310
C. This mass loss is independent of the heating rate. Addi- prevent the spread of fire to other materials. Typically, fire-
tionally, the apparent activation energy of 160e170 kJ/mol was retardant natural fibres undergo two primary approaches: rein-
recorded for these natural fibres. These data allow the development forcing the fibres or applying a protective coating. These treatments
of a simplified methodology to better identify the thermal degra- enhance the bonding between the fibre and matrix, thereby
dation behaviour of natural fibres in polymer composite processing improving the molecular structure of NFPC, or reducing heat
[74,75]. Furthermore, the degradation mechanisms of each transfer within the composite. One way to classify fire retardancy
component presenting in biofibres, such as water, extractives, techniques for natural fibres is based on their durability level. For
8
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 7. Thermal decomposition of the natural fibres and their components (e.g., hemicellulose, cellulose, and lignin) [8,67e69].

instance, textiles and fibres requiring washability require a durable nonwoven goods. Among different materials borax and boric acid
fire-retardant finishing. This approach may involve a chemical re- are the most common flame retardants [82]. In this regard, a flame
action between the hydroxyl groups of cellulose in the fibres and retardant in the presence of a binder can be applied to the textiles
the functional group of reactive flame retardant [76]. In this using back-coating techniques such as knife over air, knife over
context, allowing chemical agents access to the crystalline regions roller, and a lick roller. Furthermore, a straightforward dipping and
of cellulose is a fundamental requirement for chemical modifica- squeezing process can impregnate textiles/fabric with flame re-
tion. This can be achieved by pre-treatment with aqueous solutions, tardants [83]. Semi-durable flame retardants are designed to
leading to cellulose swelling and thereby creating pathways for the withstand a limited number of washes but may experience a
penetration of chemical agents [77]. The functionalisation of gradual reduction in flame retardancy after each wash. Common
lignocellulosic fibres involves adding water and alkalis, esterifica- materials such as urea and ammonium polyphosphate have
tion, etherification, oxidation, and other reactions including cold demonstrated effectiveness for fabrics however some semi-durable
plasma, halogenation, and corona treatment [78e81]. In contrast to flame retardants may exhibit poor stability during laundering. For
durable fireproof finishing, non-durable flame retardancy is less instance, semi-durable flame retardant finishes based on inorganic
resistant to degradation after washing. Due to this characteristic, phosphates cannot resist alkaline laundering conditions [84]. The
non-durable flame retardants are typically employed in products details of the abovementioned treatments are reported in the
intended for single use, such as disposable cotton mats and literature [82] and briefly illustrated in Fig. 8.

9
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Table 2
DTG data of biomass samples [72].

Fibre First stage Second stage

Name Tpeak (
C) Temperature range (
C) Tpeak (
C) Temperature range (
C)

Cellulose 338 300e360 e e

Lignin e e 548 450e600
Almond shell 298 250e390 477 400e720
Apple tree leaves 311 220e350 414 410e600
Beetroot pellets 342 210e380 541 400e640
Briquette 343 260e400 509 410e550
Charcoal e e 490 400e900
Chestnut tree chips 335 260e370 473 400e520
Cocoa bean husk 312 225e350 627 425e634
Coffee bean husk 319 220e360 502 440e520
Corncob 289 250e340 454 400e550
Eucalyptus tree chips 340 250e370 486 420e520
Extracted olive pomace 328 230e360 550 400e725
Gorse 339 250e390 560 450e570
Grape seed flour 340 255e375 546 400e775
Miscanthus 307 240e340 550 450e550
Olive stone 340 260e360 418 400e820
Olive tree pruning 342 250e375 469 430e570
Pepper plant 311 220e374 460 400e807
Pine and pineapple leave pellets 324 250e360 422 400e740
Pine kernel shell 249 270e370 515 400e820
Pineapple leaf 344 250e380 496 420e570
Rice husk 334 260e360 450 400e540
Sainfoin 301 230e330 456 390e522
Scrubland pruning 334 260e370 538 400e760
Thistle 345 240e400 473 420e550
Vine shoot 318 250e380 468 420e500
Wheat straw 312 260e360 543 420e650
Wheat straw pellets 300 230e365 458 400e528

Fig. 8. Different flame-retardant treatments on natural fibre/fabrics.

10
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

In addition to the chemical modification, the recent advances in at exposed surfaces from heat fronts. Nonetheless, the effect of the
genetic science resulted in cellulosic materials with built-in flame char on structural integrity is still a concern. For example, starch in
retardants. Researchers at the U.S. Department of Agriculture's starch-based thermoplastic can contribute to the char formation in
(USDA) Agricultural Research Service (ARS) produced four cotton NFPCs [111]. Polymer matrices with the potential of network for-
lines that can be utilised to make self-extinguishing fabrics when mation such as thermosets and malleable vitrimers prevent the
exposed to flame; therefore, there will be no need for flame re- flowability of the matrices at high temperatures, compared to the
tardants to be embedded in products [85]. According to the pro- thermoplastics. In other words, when it comes to the thermoset-
cessing type, the method of flame retard finishing is classified into based NFPCs, the material's structural integrity usually with-
six primary techniques including pad-dry-cure, sol-gel method, stands high temperatures until reaching the complete degradation
plasma technology, UV-curing technology. Table 3 displays of the NFPCs. Although the structure collapse is delayed, the flame
different approaches for chemically or physically modifying natural has more access to the material, leading to considerable smoke
fibers to enhance their fire retardancy, along with the corre- production. Thermoforming materials such as thermoplastics tend
sponding testing results and standards. to drip when exposed to fire. While the combustion zone can fully
or partially be removed from the surface, leading to fire suppres-
4. Flammability behaviour of NFPCs sion, it's important to note that this dripping behaviour can influ-
ence the propagation and spread of the fire within the
Despite the renewability, eco-friendliness, low cost, and superior environment. The extent to which the fire spreads can depend on
mechanical performance of NFPCs, strict fire safety policies have whether the dripping material carries a flame. Additionally, the
restricted the use of biocomposites in high-temperature applica- thermoforming behaviour of the thermoplastics can expose the
tions where the thermal stability of natural fibre plays a crucial role. core of the NFPCs including fibres, to the combustion zone, which
To overcome this concern, a wide range of natural fibre-polymer can facilitate the char formation on the one hand and debonding of
combinations have been combined with flame-resistance mate- the fibre from the matrix on the other hand. These adverse mech-
rials such as halogenated and non-halogenated flame-retardants, anisms occur simultaneously during combustion processes; dis-
layered silicates, grafting, nanofillers, copolymerization, and syn- tinguishing each is complicated. For vitrimers, it is essential to
ergistic incorporation of natural fibre and fire retardant through highlight that their plasticity behaviour is solid-state in nature, and
chemical and or physical treatments. Although these modifications they do not exhibit flammable dripping, especially when formu-
have enhanced the flame resistance behaviour of NFPCs, they still lated with inherent flame retardant properties in their precursor
need to comply with stringent fire safety regulations in aerospace materials during synthesis [112e114]. This characteristic makes
and automotive industries such as the code of Federal Aviation vitrimers a promising choice in applications where mechanical
Regulation 25.853 and the Federal Motor Vehicle Safety Standard. properties and fire resistance are crucial considerations. Generally,
Therefore, there is a need for a comprehensive investigation of the the thermal conductivity of the NFPCs is the function of composites
thermal stability/degradation and flammability/fire behaviour of conductivity values, fibre volume fractions and the orientation of
NFPCs while maintaining structural integrity. the fibres [115]. When the fibres align parallel to the NFPC, the fi-
bres restrict the transfer of thermal heat from getting into the
4.1. Parameters affecting the flammability of NFPCs composite [116]. Similarly, numerous efforts have been made to
exhibit the effective thermal conductivities (ETC) of NFPC [117,118].
As shown in Fig. 9, there are different factors affecting the Interestingly, it was observed that the thermal stability of the
flammability of NFPCs. These factors are classified into two main multi-angled laminate was identified to be higher than that of the
groups including internal factors and external ones. Internal factors unidirectional fibres. This can be ascribed to the fact that multi-
are dealing with properties of each component of NFPCs. These aligned fibres in a laminate are more closely packed, thus acceler-
components consist of reinforced phases (e.g., matrices), primary ating the heat conduction process across the laminates [119].
reinforcing phases (e.g., natural fibres), secondry reinforcing phase Concerning fibre orientation, Simran Dutt Sharma et al. [120]
(e.g., additives), and interphase. However, external factors cover examined the effect of different fibre orientations on heat transfer
fabrication techniques, processing parameters considered during in fibre-reinforced polymer composite regimes under transient
fabrication as well as the application situation (e.g., end-use con- conditions. They used finite element method simulations to visu-
ditions). With respect to internal factors, different polymers have alise and model fibre-reinforced matrix composites 2D micro-
been utilised to fabricate NFPCs to reinforce matrices against shear structures with thermal conductivity. The heat transfer analysis has
and compression forces. These matrices can be classified according been performed for various microstructural topologies by creating
to their degradability level into fully degradable or partly degrad- different arrangements of fibre insertion within the matrix and
able matrices. Fully degradable matrices can be natural-based their heat transfer response. It was implied that microstructural
chemicals such as polylactic acid, thermoplastic starch, cellulose, conglomeration significantly impacts thermal conductivity, and
and polyhydroxy alkanoate or oil-based chemicals including consequently, the thermal conduction of the composite is affected
aliphatic polyester, aliphatic-aromatic polyester, polyester amid, by rotating fibres in the matrix. They found that the time for
poly alkyne succinate, and polyvinyl alcohol. However, poly- saturation is inversely related to the conductivity of the fibre-
propylene, polyester, and polyethylene are some of the partly reinforced polymer composite. Also, the fibre arrangements with
degradable matrices used in NFPCs fabrication. Polymers with square diagonal arrays give more heat transfer resistance, as the
higher biodegradability generally show insufficient thermal sta- saturation time is more significant than in the other two cases. As
bility and mechanical performance-hence more vulnerable to illustrated in Fig. 9, in addition to the orientation of fibre, the
flammability. The polymers with higher biodegradability cannot loading level of fibre in NFPCs can also affect the thermal stability
compete with the conventional polymers used in high- and flammability behaviour of NFPCs. Increasing the fibre volume
performance applications such as automobile or aerospace where fraction in NFPCs improved mechanical properties and reduced the
the function of load-bearing is crucial [110]. One of the advantages linear burning rate [121]. It is believed that a higher volume fraction
of biodegradable polymers as polymer matrices is their char- of natural fibres such as flax [122], jute [123], and wood can result
forming potential. In other words, although biodegradable poly- in earlier and shorter ignition times. Still, it can considerably reduce
mers show poor thermal stability, they can facilitate carbonisation the PHRR, average MLR, and smoke/gas emissions.
11
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Table 3
Comparison of different fire/flammability test techniques used in literature.

Natural phase Type of test Flame retardant Test results/ratings/standards Reference

Bamboo fibre UL-94a SiN hybrid aerogel, ammonium polyphosphate V0 [86]

ASTM D3801-20A
Ramie fibre Aluminium diethyl phosphinate, melamine V1 and V0 [87]
cyanurate, silica GB/T2408-2008
Woven Jute fibre Fly ash and NaOH treatment. V1 [88]
ASTM D635 and D3801 for horizontal and
vertical protocols
Bamboo fibre Chitosan-based bio-flame retardant based on HB n/a [89]
chitosan and silica
Cellulose nanocrystals Glycidoxypropyltrimethoxysilane and 10-dihydro- V2 [90]
9-oxa-10-phosphaphenanthrene 10-oxide ASTM D-3801
Wood Poly [N4-bis(ethylenediamino)-phenyl phosphonic- V0 [91]
N2,N6-bis(ethylenediamino)-1,3,5-triazine-N- ASTM D3801
phenyl phosphonate] and ammonium
polyphosphate
Wood flour Cone calorimeter A single flame retardant of ammonium Tign change (%): þ33 pHRR change (%): 40 [92]
polyphosphate (APP) modified via ion exchange THR change (%): 36 n/a
reaction with ethanolamine
Flax nonwoven Sodium Alginate Tign change (%): 60 pHRR change (%): 12 [93]
THR change (%): 11
Lignin waste Polyphosphoramide Tign change (%): 12 pHRR change (%): 6 [94]
THR change (%): 10
ISO 5660
Flax fibre Aluminium diethyl phosphinate Tign change (%): 50 pHRR change (%): 20 [95]
THR change (%): 21
ISO 5660-1
Wood flour Oxidation of wood flour and the use of ammonium Tign change (%): 35 pHRR change (%): 31 [96]
polyphosphate THR change (%): 22
ISO 5660-1
Bamboo flour Boric acid Tign change (%): No pHRR change (%): 26 [97]
Ammonium polyphosphate THR change (%): 2
Silicon dioxide ISO 5660
Coffee husks (Lignocelluloses) LOI Phytic acid/amine silane 26.7% n/a [98]
Rice straw (Cellulose nanofibrils) Nanoplatelets of expanded graphite 44% [99]
ASTM D2863
Pine flakes Calcium carbonate 37% [100]
GB/T 2406.2e2009
Water hyacinth fibre Ammonium polyphosphate 29.2% [101]
ASTM D2863
Pinecones Boron oxide 22% [102]
ASTM D2863
Timoho fibre Iron powder 28.9% n/a [103]
Flax fabric PCFC Sodium polyacrylate Polyethylenimine pHRR changeb (%): 80 [104]
Ammonium polyphosphate THR changeb (%): 64
Char yield (%): 31
Method A- ASTM D7309
Flax fibre A phosphorus-based dimethyl (methacryloxy) pHRR changeb (%): 73 [105]
methyl phosphonate THR changeb (%): 71
Char yield (%): 43
Method A- ASTM D7309
Cotton fabric Kaolinite-TiO2 pHRR changeb (%): 86.9 [106]
THR changeb (%): 77.2
Char yield (%): 45.06
ASTM 7309-07
Bamboo fibre Ce-doped titanate nanotubes pHRR changeb (%): 86.9 [107]
THR changeb (%): 77.2
Char yield (%): 45.06
ASTM 7309-07
Flax fabrics Vinyl phosphonic acid pHRR changeb (%): 77.4 [108]
THR changeb (%): 78.5
Char yield (%): 37.8
ASTM 7309-07
Jute fabric Chitosan and sodium alginate pHRR changeb (%): 48.2 [109]
THR changeb (%): 44.45
Char yield (%): 28.9
ASTM 7309
a
Almost all reference samples are not rated in the UL-94 test.
b
The values are compared to the untreated fabric/fibres as references.

12
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 9. Internal and external factors affecting the flammability of NFPCs.

Researchers have incorporated other micro/nano-sized mate- indicates that the production of NFPCs is compatible with industrial
rials into the matrices to introduce multifunctionalities to natural production [136].
fibre composites. These micro/nano-sized secondary re- Compared to synthetic fibres, the durability of natural fibre can
inforcements not only improve the mechanical properties but also be highly affected by humidity, hydrothermal, and weathering
present the NFPCs with enhanced wear [124], flame, thermal [125], conditions. Additionally, since natural fibre shows poor fire resis-
vibrational [126], antifungal [127] and EMI shielding properties tance, its applications in aviation and automotive face various
[128]. Regarding flame properties, micro/nano-sized materials in challenges. While NFPCs offer lightweight solutions for the aviation
polymer matrices exhibit higher content than other micro/nano- and automotive industries, meeting stringent fire safety regulations
sized materials. Achieving a well-dispersed and evenly distrib- requires NFPCs to have robust fire resistance properties. However, a
uted morphology is crucial. Failure to do so can have a detrimental high content of flame retardants, particularly inorganic ones, can
impact on the mechanical properties of NFPCs. Therefore, the sec- lead to increased structural weight, higher fuel consumption, and
ondary reinforcements can be functionalised to improve their more significant carbon emissions. This outcome contradicts the
compatibility with matrices through chemical approaches or ecological principles underlying the use of NFPCs.
compatibilisers [129e131]. In addition to the challenges of homo- Furthermore, reducing the content of flame retardants may limit
geneity level, the rheological properties of matrices, including the effectiveness of flame retardancy in NFPCs. As a result, they may
thermosets and thermoplastics can be affected by the high content find application primarily in non-engineering contexts where fire
of flame-retardant additives. A higher viscosity leads to poor safety regulations are less stringent [137].
penetration of matrices into the natural fibre structure and there-
fore poor wettability. As a result, defects will be generated at the 4.2. Flammability mechanisms in NFPCs
interfacial areas between natural fibre and matrix, reducing me-
chanical and thermal properties [131,132]. Nevertheless, some The combustion of NFPCs involves the degradation of natural
thermoplastics' higher flame retardant content can promote shear fibre and polymer matrix, as illustrated in Fig. 10., starting with
thinning behaviour [133,134]. initial discolouration and concurrent structure weakening, even-
On the other hand, external factors such as the fabrication tually progressing to blackening and blistering. The thermal
methods and processing parameters can determine the ultimate degradation process of NFPCs undergoes a complex sequence
performance of NFPCs. The fabrication of NFPCs involves the beginning with an initial discolouration and concurrent, structure
collaboration of fibre and matrix at sufficiently high temperatures weakening, eventually progressing to blackening and blistering.
and shear forces which can potentially lead to degradation of the Generally, NFPCs experience moisture evaporation due to the hy-
NFPCs. During NFPC fabrication, the structure and properties of drophilic nature of natural fibre and the release of gaseous products
both matrix and fibre are affected, [135]. Concerning natural fibre- at temperatures between 150
C and 250
C. It is also highly likely
reinforced thermoset composites, hand lay-up, compression that pressure becomes trapped in gas pockets just below the sur-
moulding, resin transfer moulding, pressure bag moulding, pul- face of the NFPCs [138]. Meanwhile, the polymer matrix should also
trusion, vacuum-assisted resin transfer moulding, casting injection decompose into more minor components that can migrate from the
moulding, and polyurethane foam moulding have been used. bulk of the material into the gas phase. In contrast, the high mo-
Rotational moulding, calendaring, coextrusion, filament winding, lecular weight components remain in the condensed phase. Once
thermoforming, injection moulding, and compression moulding the combustion of these volatile gases generates sufficient heat it
methods have been used to fabricate natural fibre-reinforced initiates a self-sustaining reaction. The polymer can experience two
thermoset composites. The variety of production techniques different degradation streams in both main and side chains. Main
13
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 10. Degradation mechanism in NFPCs.

chain reactions deal with chain session and cross-linking, whereas intumescent. The compact char has better barrier properties and
side chain reactions involve side chain elimination and side chain acts as an insulation layer to keep the fresh surface of NFPCs safe
cyclisation. The thermoset resin does not experience phase change from the combustion heat. This can result in a reduction of PHRR
and only experiences water desorption and charring, whereas and THR [143].
thermoplastic can experience a rubbery, melting, and viscous state. As illustrated in Fig. 11, during the combustion process, there is a
Compared to the polymer matrix, cellulose materials also undergo close correlation between the flammability behaviour or fire
semi-physical transformation related to the desorption of chemi- retardancy performance and mechanical properties, which are
cally/physically absorbed water [139]. More specifically, the natural affected by matrix/fibre and the types of flame-retardant materials.
materials in NFPCs have low thermal conductivity and density but These two factors influence each other and lead to varying post-fire
relatively high specific heat. During the degradation, they generally properties and flammability behaviour. In this context, the primary
experience three main stages: dehydration, slow pyrolysis below concern revolves around the time it takes for the burning structure
200
C, initiation of pyrolysis around 300
C, and rapid degradation to deform and collapse, specifically when they are load-bearing
above 300
C [140]. Furthermore, as the main component in natural structures. The premature collapse of either the entire structure
material, cellulose initially undergoes a phase known as the or a specific section can promote flammability and provide access
“molten-phase intermediate” or “active cellulose”. The active cel- to underlying layers of materials. Based on this fact, measuring the
lulose involves two competitive weight loss reactions: high- flame-mechanical properties correlation can accurately predict the
temperature depolymerisation and low-temperature secondary flammability mechanism. The most reliable approach for
reactions. The former leads to the formation of volatile species and measuring the effect of flame on the mechanical properties of
the latter results in the formation of carbon dioxide, steam, and composite materials is full-scale, quarter-scale room, and extensive
char [141]. Once the heating process proceeds further, the hydro- panel burn tests. The general procedure for these tests involves
lysed components undergo chemical dehydration, decarbonylation, exposing the large composite structures to a high-temperature
decarboxylation, cross-linking and aromatisation reactions that flame. Once the fire is distinguished, the residual mechanical
form solid primary char [142]. The char formed on the material's properties of burnt composites are evaluated. Generally, these
surface can be affected by the type of polymer, natural fibre, and testing methods are expensive and time-consuming [144]. As dis-
flame retardants. The char can be compact or porous and form a cussed in the previous section, although the cone calorimeter test is
protective coating onto the material's surface in the form of significantly cheaper, faster, and highly feasible, this test is not

14
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 11. The schematic of the factors/mechanisms affecting the flammability behaviour of NFPCs.

designed to investigate the mechanical properties reduction after mechanical properties [149]. Another factor affecting the structural
fire. The cone calorimeter test deals with indirect flame ignition integrity of natural fibre composite is related to the release rate of
and irradiation of the material with high heat flux and does not deal smoke and volatile material and their densities in these compos-
with direct exposure to fire. Additionally, in the actual fire scenario, ites. The release of the volatile can build up pressure inside the
there is a flashover and temperature fluctuation that this test material, making it more conspicuous when compacting the char.
cannot simulate [144e146]. The thermal strain can form char in Therefore, the mechanical properties are more susceptible under
natural fibre composites, indicating mechanical properties. In other these circumstances. However, the high smoke and the smoke
words, the higher char formation is defined as high material density indicate that the flame-retardant acts efficiently in the gas
degradation and lower retention of mechanical properties. None- phase; therefore, it can be predicted that there is lower mass
theless, it is essential to determine whether the char comes from transfer from the material to the combustion zone. Consequently,
the material's oxidation or is grown by the flame retardant. In the the post-fire mechanical properties of the material are kept intact
former scenario, the thickness reduction can generally be seen. In [150].
contrast, the latter scenario's thickness is higher because the char is
preferably formed on the utmost outer surface. The change in the 4.3. Fire retardancy techniques in NFPC
thickness can affect the mechanical strength evaluation
[144,147,148]. Nonetheless, in the real-life scenario, on the one In recent decades, fire safety regulators have begun considering
hand, the thickness of the material can increase due to the factors beyond the materials' flammability when evaluating
expansion and char formation; on the other hand, the material can structural fire resistance products. In other words, there is a de-
show shrinkage during the degradation, leading to the thickness mand for products that combine outstanding flame resistance with
reduction. Additionally, when the NFPCs catch fire, the material's high mechanical performance. It has been predicted that the
delamination leads to additional core exposure to fire, acting as structural and mechanical integrity of the materials can, to a great
fuel. Therefore, it can be concluded that the higher heat release rate extent, pinpoint the ultimate tolerance of the materials during
of the material indicates the extent of fire damage to the backbone service and precisely when they are exposed to fire. Although
of structural natural fibre composites and its impact on the postfire polymer composites have shown superior mechanical properties
15
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

thanks to their reinforcing phase (e.g., fibres), the high content of [161]. Several reports in the literature investigate nanomaterials'
flame retardants makes them vulnerable towards abrupt failure. influence on the fire retardancy performance of composites. For
Additionally, such phenomenon is more conspicuous in natural example, Khalili et al. [162] showed that the addition of high con-
fibre composite due to their high sensitivity to polymeric medium tent of expandable graphite (5 wt%) in natural fibre-reinforced
and their lower inherent mechanical strength. epoxy composites could weaken the wettability of the fibre by
As a result, the performance index has been defined for various the epoxy and worsen the interfacial adhesion, leading to the for-
composites to determine the maximum amount of flame retardant mation of micro-cracks as illustrated in Fig. 12a and b. However,
that can be incorporated into the material without compromising incorporating the flame retardants through surface coating
its mechanical performance. In other words, the performance index enhanced mechanical performance by improving the chemical
is a correlation between one characteristic of mechanical properties reactivity of the components (e.g., fibre and matrix) at the interface.
(e.g., ultimate tensile strength) and one characteristic of flame Yang et al. observed that the interface of polylactide and corn fibres
property (e.g. PHRR) as follows [151]: could be improved by surface coating of fibres with a biobased
flame-retardant material synthesised from Trometamol and phytic
acid. They declared that incorporating the modified fibre can
Performance index ¼ ðMechanical proeprtyÞn
decrease the debonding holes at the interface and change the flat
 ðFlame retardance propertyÞ1n fracture morphology of the matrix to a rough morphology, Fig. 12c
and d [163]. In another study by Zhang et al. [164], the neat flax
Where n is defined as the importance weight of each component, fibre was initially coated with a thin polydopamine film, followed
which lies between 0 and 1. by in situ growth of iron phosphonate on the fibre surface. They
Generally, two approaches can be pursued to impart flame observed that although such a modification could improve the
resistance to NFPCs. One process involves the incorporation of flame resistance of polylactic acid composites, the poor interfacial
flame retardant into the matrix; the other method deals with adhesion between the modified fibre and matrix could result in
modifying the fibre surface with flame resistance agents in the form fibre bundle pullout and the deterioration of the mechanical
of functional groups or flame resistance particulates. In either of properties, Fig. 12e and f. Ali et al. [165] showed that the addition of
these methods, the interface plays a key role. In other words, fire ammonium polyphosphate and graphene into the flax poly-
resistance composites, including flame retardants in composites, propylene composites resulted in interrupting the interfacial
can affect the interface closely connected to the mechanical prop- adhesion between fibre and polymer, which leads to the formation
erties. Various types of flame retardants have been used in this of microcracks, resulting in interfacial failure of the composite.
regard, and these flame retardants improve the flame resistance Nonetheless, these additives' elevated stiffness and particulate
behaviour of the NFPCs through multiple mechanisms, including characteristics can enhance the modulus, thereby improving
physical dilution [152], chemical interactions [153], inert gas, and interfacial adhesion, Fig. 12g and h. In a study conducted by Dou
thermal quenching and char formation [154,155]. Introducing et al., the enhanced tensile and flexural strengths of jute fibre/
various flame retardancy mechanisms requires the use of diverse polypropylene composites were attributed to the ability of
flame retardants. ammonium polyphosphate, melamine, b-cyclodextrin and the
The flame retardants can be halogenated additives such as polypropylene matrix to create a comprehensive and uniform
bromine and chlorine, capturing the free radicals and reducing fire flame-retardant layer during of flame-retardant layer during the
propagations [156]. They can also be synthesised based on phos- hot-pressing process. Jeencham et al. [166] used various flame re-
phorous compounds such as phosphonates, phosphate esters, and tardants including ammonium polyphosphate, magnesium hy-
phosphinates acting as char former and enhancers in the droxide, and zinc borate in sisal fibre/polypropylene composites.
condensed phase [157]. Additionally, there has been an increased They observed that the content of flame retardants and the surface
interest in using nitrogen-based flame retardants since they are morphology of flame retardants influences the mechanical prop-
considered low-toxic flame retardants. For example, melamine erties. In other words, they showed that incorporating magnesium
polyphosphate, melamine cyanurate, and melamine poly (zinc/ hydroxide and ammonium polyphosphate does not considerably
ammonium) phosphate can release nitrogen gases as a cooling affect the composites' tensile properties. In contrast, including zinc
agent or promote char formation in the condensed phase [158]. As a borate enhanced the tensile strength due to the higher surface
rival to nitrogen-based flame retardants, silicon-based flame re- roughness of zinc borate compared to magnesium hydroxide and
tardants such as silica, silicates, silicon, and silane have been used ammonium polyphosphate. As a result, this promotes mechanical
for a long time. They can significantly contribute to the char for- interlocking between zinc borate and polypropylene matrix,
mation in the condensed phase. Additionally, diluting high- ensuring that the flame retardants do not adversely affect the
temperature gases and scavenging the free radicals are other mechanical performance of the composites.
flame-retardant mechanisms for these materials [159]. Compared Fig. 13 shows the PHRR, THR, and tensile strength of various
to micron-sized flame retardants, nanomaterials based on carbon- natural fibre-reinforced composites, including varying content of
carbon structures such as carbon nanotubes and graphene can flame retardants. Flame retardant in natural fibre-reinforced com-
considerably promote thick char due to high surface area and low posites generally reduced THR, PHRR, and tensile strength. It is also
filler-to-filler distance. The high thickness of char can prevent ox- clear that in most cases, except the hybrid combinations, the con-
ygen from reaching the fresh underlying semi-polymerised poly- tents of flame retardant in natural fibre composites are quite high.
mer. These nanomaterials improve not only the flame properties Such a high flame retardant content can have a devastating effect
but also the mechanical properties, making them exceptional. on the tensile properties of composites due to poor dispersion and
Graphene, specifically, can create thermal bridges to conduct heat interfacial interactions. Nonetheless, due to the high flame retar-
on one hand. On the other hand, their large lateral dimension can dant content, most biocomposites have shown the V0 rating in the
also create tortuous pathways, which is highly effective for retar- UL-94 test, except for a few samples rated V1 and V2. It is also
dation of flame and crack propagation [160]. Like graphene, evident that compared to the conventional flame retardants, which
nanoclay can decrease the heat release rate and enhance the carbon are generally based on phosphorus and amino silane compounds,
monoxide yields and smoke. Nanoclay can increase polymer vis- the hybrid flame retardants show better mechanical reinforcing
cosity at high temperatures, preventing the polymer from dripping potential in biocomposites, as illustrated in detail in Table 4,
16
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 12. SEM of tensile fractured morphology of alkali-treated pulverised oil palm empty fruit bunch fibres/epoxy composites (a) without (b) with expandable graphite [162]; SEM of
impact fractured morphology of oxidised corn pith fibre/polylactide composites (c) without (d) with biobased coating on fibre [163]; SEM of tensile fractured morphology of flax
fibre/poly lactic acid composites (e) without (f) with iron phosphonate coating on fibre surface [164]; SEM of tensile fractured surfaces of flax-polypropylene composites (g) without
(h) with ammonium polyphosphate and graphene [165]. SEM micrographs of tensile fracture surface sisal fibre/polypropylene including (a) ammonium polyphosphate/magnesium
hydroxide and (b) ammonium polyphosphate/zinc borate [166].

indicating the composites can take the advantages of rigid nature of NFPCs once they have fulfilled their service life [186e188]. Recy-
nanomaterials such as graphene, nanoclay, and carbon nanotubes. cling NFPCs presents challenges and deficiencies related to the
behaviour of individual components such as matrices, re-
5. Sustainability and recycling aspects of NFPCs inforcements, and additives, which will be discussed in the
following sections.
The abundant availability, low density, minimal health concerns, As depicted in Fig. 14, during the recycling process of NFPCs, a
biodegradability, and technical feasibility of natural reinforcements wide range of properties transform. These include thermal char-
(e.g., natural fibres) position them as eco-friendly alternatives to acteristics, mechanical attributes, degree of crystallisation, hygro-
replace unsustainable reinforcements like carbon and glass fibres, scopic behaviour, weathering resistance, UV resistance/durability,
offering benefits across various applications. However, their limited and rheological and viscoelastic properties. It is generally observed
lifespan underscores the necessity for recycling and repurposing that recycled NFPCs exhibit reduced performance compared to
17
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 13. The effect of flame-retardant content on THR, PHRR, and tensile strength of natural fibre-reinforced composites [129,144e147,149e151,155,162e185].

their original counterparts. To address this issue, various additives, NFPC fabrication include polymers with low processing tempera-
such as processing aids, flame retardants, strengthening agents, tures, such as polyethylene, polypropylene, polyamides, polyvinyl
stabilisers, antioxidants, and chain extenders, have been exten- chloride, and polylactic acid. These low processing temperatures
sively employed. These additives function the recycled NFPCs, help prevent the thermal degradation of natural fibres. Various
imparting new capabilities and enhancing their overall perfor- mechanical and thermal recycling methods have been employed
mance [189]. for NFPC recycling. However, these methods are often neither
Once their service life has ended, incorporating thermoplastics cost-effective nor practical. Consequently, NFPC waste is often
as matrices in NFPCs can provide the advantage of recyclability. incinerated for energy or disposed of in landfills. Recycling and
Thermoplastic NFPCs can typically undergo recycling for four to six repurposing NFPCs involve a rigorous reprocessing stage that can
cycles before their quality deteriorates, so they can no longer be impact various properties of NFPCs, including their mechanical,
effectively used. Recyclable thermoplastics commonly used for thermal, and viscoelastic properties.

18
 Table 4

M. Ahmadi, O. Zabihi, Z.K. Nia et al.

Different types of flame retardants affect the mechanical performance of natural fibre composites.

Type of fibre Type of flame retardant Type of matrix Sample preparation Mechanical properties Comments Ref.
method

Flax (30 wt%) Aluminium trihydroxide þ zinc Polypropylene Mixing by extrusion and 35% drop in tensile strength. 46% The reduction of elongation resulted in [151]
borate þ ammonium internal mixer increase in tensile modulus the reduction of impact properties. A
polyphosphate (60 wt%) high shear rate can highlight the effect
of particle size on mechanical
properties, but it can damage the
natural fibre.
Alkali-treated Expandable graphite. (5 wt%) Epoxy Mechanical mixing 24.77%, 51.26%, and 28.8% increases in The addition of fibre increases the [162]
pulverised oil palm followed by ultrasonication tensile strength, elongation at break, ductility of the matrix. Expandable
empty fruit bunch and the use of compression and modulus compared to the samples graphite interrupts the load transfer
fibres (20 wt%) moulding. reinforced with only 20 wt% of from epoxy to fibre.
untreated fibre.
Oxidised corn pith fibre Biobased flame retardant Polylactide Melt-mixing and hot press. 3.22%, 0.74%, and þ11.11% changes The small flame retardant content [163]
(10 wt%) through coating method. (5 in elongation at break, tensile, and showed little effect on the crystallinity
phr) impact strength. of the composite.
Flax fibre (30 wt%) Thin adhesive polydopamine Polylactic acid Micro compounding and 7.82% and 14.7% changes tensile The reduction of fibre length during the [164]
coating followed by in situ hot compression moulding. strength and Young's modulus. chemical modification decreased
growth of iron phosphonate. tensile strength.
Flax fibre (24.75 wt%) Ammonium Polyphosphate Polypropylene Twin-screw extruder for Increase in tensile strength and The addition of flame retardant reduced [165]
(14.85 wt%) melt blending modulus by 3.43% and 44.88%. 10.1% the mechanical properties. The
þ Graphene (1 wt%) and 10% changes in flexural strength graphene resulted in high-stress
and modulus. transfer at the interface.
Jute fibre (Fibre to Ammonium polyphosphate, Polypropylene Hot press þ6% and 24.12% increases in tensile and The reaction between the char agent [169]
matrix weight ratio melamine, and b-cyclodextrin flexural strengths. and ammonium polyphosphate
1:1) as a char agent. (20 wt%) improved char ability formation.
Sisal fibre (30 wt%) Ammonium polyphosphate Polypropylene Melt mixing with an 0.58%, 6.25%, and 25.17% changes in The addition of flame retardant changes [166]
19

(30 phr) þ Magnesium internal mixer tensile strength, tensile modulus, and the ductile behaviour of the matrix into
hydroxide (10 phr) impact strength. a brittle one.
Ammonium polyphosphate 1.34%, 4.33%, and 23.53% changes in The addition of flame retardant resulted
(30 phr) þ Zinc borate (10 phr) tensile strength, tensile modulus, and in strain reduction.
impact strength.
Palm oil empty fruit Ammonium polyphosphate Epoxy Ultrasonic dispersion The reduction of flexural strength, The failure of samples started with a [155]
bunch fibre (20 wt%) (10 wt%) þ Zinc borate (5 wt%) instrument and vacuum flexural strain, ultimate tensile crack on the tension side and grew until
resin infusion method strength, and elongation at break complete failure.

Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

by 2.5%, 16.8%, 20%, and 14%.
The increase
Pulverised palm fibre Alumina trihydrate (10 wt Epoxide resin Resin infusion 34%, 5.3%, and 24.69 changes in The poor compatibility between [172]
(18 wt%) %) þ Ammonium tensile strength, Young's modulus, and ammonium polyphosphate and
polyphosphate (5 wt%) Elongation at the break. 30.7% and polymer matrices resulted in property
44.62% changes in flexural strength and reduction.
failure strain.
Kenaf bast fibre (30 wt Halloysite nano-tubes (HNT), Polypropylene þ ammonium High-intensity mixer by 19.3% and 9.2% decreases in tensile The addition of flame retardant [129]
%) montmorillonite nanoclay poly-phosphate (20 wt%) twin-screw Extruder strengths; 11.31% and 25.99% interrupts the interfacial stress transfer.
(MMT), decreases in flexural strengths; 34.6% The additives can act as nucleating sites
(3 wt%) and 39.3% decreases in impact for for improving the crystallinity
samples including HNT and MMT, behaviour.
respectively.
Sisal (30 wt%) Nanoclay, Epoxy High-pressure mixing and 7.56%, 12.75%, 6.11%, 2.72%, and 3.62% The good interfacial interaction [176]
Bis (2-hydroxy-ethyl) methyl compression moulding increase in tensile strength, tensile between the alkylammonium ion
tallow ammonium modulus, flexural strength, flexural groups of nanoclay and the matrix. The
(1 wt%) modulus, and impact strength. improvement of roughness and
adhesive features of the sisal fibre
surface
(continued on next page)
 Table 4 (continued )

M. Ahmadi, O. Zabihi, Z.K. Nia et al.

Type of fibre Type of flame retardant Type of matrix Sample preparation Mechanical properties Comments Ref.
method

Hemp (30 wt%) Phosphoric acid þ aminosilane Epoxy Hand lay-up technique 2.2%, þ20.85%, 5.7%, and 5.9% Neither fibre-pull outs nor [181]
(8 wt%) changes in tensile strength, tensile delamination has been observed.
modulus, flexural strength, and flexural
modulus.
Kenafþ Ammonium polyphosphate Polypropylene Extrusion and injection þ18.4%, þ10.6%, 17%, 37.2%, The orientation of the fibre can improve [180]
Wool (33 wt%) (20 wt%) moulding and 12.17% changes in tensile, the tensile modulus. Ammonium
flexural, tensile, impact, and flexural polyphosphate can act as particle
strength. reinforcements. The reduction of fibre
Wool (30 wt%) Ammonium 4.1%, þ10.2%, 23%, 31.3%, length and particle agglomeration
polyphosphate þ ultraviolet ray and 13% changes in tensile, flexural, resulted in strength reduction.
stabiliser and colourant tensile, impact, and flexural strength.
combination (30 wt%)
Flax (60 vol%) Organophosphate (7.2 wt%) Poly (lactic acid) Melt-pressing 12.9%, 57.6%, and 26.54% changes The tensile properties are fibre [179]
tensile modulus, tensile strength, and dependent. The acidity of flame
flexural modulus retardant solution can have a
devastating effect on mechanical
performance.
Wool (30 wt%) Ammonium polyphosphate Polypropylene Melt-blending process 26.24%, 4.1% changes in tensile The low aspect ratio and hydrophilicity [174]
(20 wt%) strength, tensile modulus of ammonium polyphosphate resulted
in weak interfacial adhesion.
Ramie (49.7 wt%) Phosphorus- and nitrogen- Unsaturated polyester Hand lay-up/oven vacuum 10.13% drop in tensile strength A strong interfacial interlocking can be [167]
containing silane coupling bag manufacturing method gained because of the enhanced surface
agent þ Ammonium roughness, also increasing the adhesion
polyphosphate (10 wt%) qualities between the fabrics and the
matrix.
Wool (30 wt%) Ammonium polyphosphate Polypropylene Melt blending by extrusion 37.5%, þ16.6%, 14.28%, 19.9% The early micro-voids created by [173]
20

(20 wt%) changes in tensile strength, tensile debonding between the phases affect
modulus, flexural modulus, flexural the crack propagation, resulting in the
strength leading to the drop in mechanical
properties.
Wool (20 wt%) Phenylphosphonic Poly (lactic acid) Hot compression moulding 18.58% and 129% changes in tensile The interfacial defects and the micron [182]
3(2-aminobenzothiazole) strength and tensile modulus size pores caused by flame retardant
(3 wt%) can devastate tensile strength.
Ramie (52.2 wt%) Phosphorus-containing Unsaturated polyester The oven vacuum bag 24.42%, þ68.75% change in tensile The plasticising effect derived from the [167]

Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

cardanol-based toughing manufacturing method strength and impact strength long alkyl molecular chains can reduce
agents (20 wt%) the tensile strength.
However, the long alkyl chains of the
cardanol group led to a better impact
strength.
Flax (38.2 vol%) Guanylurea methyl Polypropylene Compression moulding 48.5%, 47%, 53%, and 47% change The cellulosic structure in fibres was [178]
phosphonate, a phosphorus- in tensile strength, tensile modulus, partially damaged by the acid solution
and nitrogen-containing flexural modulus, and impact modulus coming from flame retardant
organophosphate with a treatment. The hydrolysis of polylactic
different P:N ratio (11.2 wt%) acid in the presence of flame retardant
Flax (54.6 vol%) Guanylurea methyl Poly (lactic acid) 66.27%, 44%, 62%, and 43% can reduce its properties.
phosphonate, a phosphorus- change in tensile strength, tensile
and nitrogen-containing modulus, flexural modulus, and impact
organophosphate with a modulus
different P:N ratio (9.9 wt%)
Basalt (3 wt%) Nickel alginate-brucite-based Poly (ethylene vinyl acetate) Twin-roll mixing and hot þ20% and þ165% changes in tensile The coating resulted in the [183]
flame retardant (52 wt%) copolymers press strength and elongation at break improvement of dispersion and
compatibility.
Basalt (20 wt%) Carbon nanotube þ aluminium Polylactide Extrusion and injection 24.14%, þ3.84%, 10% change in tensile The poor interfacial interaction [184]
hypophosphite (20 wt%) moulding strength, tensile modulus, and between aluminium hypophosphite
elongation at break and matrix resulted in the brittle
behaviour of the composite.
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

[170] Increasing the number of recycling times can promote the role

[150]

[171]

[185]
of reinforcements, especially natural fibres, in reprocessed NPFCs
by boosting various properties such as fibrillation, aspect ratio,
dispersion level, processing-induced orientation, and distribution
Ammonium polyphosphate can act as a

wettability, and the role of big particles

The natural fibre at lower temperature

Fe3þ treatment can lessen the catalytic
The premature failure, deterioration of

including the formation of covalent or

restrict strong interfacial interactions,
level. However, regarding matrices, especially thermoplastics,

Boric species on the fibre surfaces

although they are thermoformable and malleable, they can expe-
as nucleating agents can reduce

rience uncontrollable crosslinked structures, molecular weight

degradation of Phytic acid.

reduction, and chain scission after being reprocessed multiple
mechanical performance.

times [190]. In this context, the detrimental behaviour of thermo-

The acid hydrolyses.

plastic matrices can outweigh the positive contributions presented
reinforcing phase.

hydrogen bonds.
by reinforcing fibres [191,192]. In a few conditions, mechanically
reprocessing can increase the crystallinity level of matrices-hence
improvement of NPFCs tensile performance [193]. Throughout the
service life of NFPCs, harsh environmental conditions can impact
the reprocessability threshold, i.e., the number of times NFPCs can
be recycled or reprocessed. In essence, the natural reinforcements
modulus, flexural strength, and flexural

modulus, flexural strength, and flexural

8.18%, 2.89%, and þ76.6% changes in

7.7% and 8% changes in tensile and

in NFPCs are susceptible to UV exposure and severe weathering,

tensile strength, tensile modulus, and
þ25% and 19% changes in tensile and

13.5%, 3.6%, 3.44%, and 5.36%

changes in tensile strength, tensile

changes in tensile strength, tensile

which can detrimentally affect their mechanical performance and

35.7%, 15.8%, 41.1%, 34.9%

increase their vulnerability to thermal oxidation during service life.

Even more concerning is that these natural reinforcements exhibit
hygroscopic properties, retaining moisture, which can lead to pre-
mature hydrolytic degradation in thermoplastics susceptible to
flexural strengths

flexural strengths

water molecules' hydrolytic attack. Therefore, while NPFCs are

impact strength

reaching their end of life (EOL), they are no longer recyclable. From
this viewpoint, the recycling potential of offcuts and waste gener-
modulus

modulus

ated during NPFC manufacturing differs from that of EOL NPFCs

[194,195]. Similar to tensile properties, the flexural properties can
also be affected by reprocessing of NPFCs. Nonetheless, flexural
properties are less affected by defects unless located on the lower
and or upper surface of the NPFCs. Also, there are shear forces while
Blending and hot press

Resin infusion method

Resin infusion method

Method and hot press

samples are exposed to flexural loads; therefore, interfacial adhe-

sion plays a pivotal role. Compared to tensile properties, chain
scission, oxidation, and formation of functional groups during aging
Hand lay-up

result in improved interfacial adhesion, and consequently, flexural

properties can be improved [191,196]. Repeated reprocessing of
NPFCs can also improve the impact properties and induce ductile
behaviour in NPFCs through different mechanisms, including
reduced fibre length, matrix stiffness, and interfacial gaps/
debonding [197,198]. Any changes in structures of reinforcing
phases and polymer matrices in NPFCs can affect thermal proper-
Unsaturated polyester

ties, including crystallisation, glass transition temperature, and

melting point. For example, the crystallinity of polymer matrices
Polypropylene

can significantly be improved for low molecular weight polymer

Elium® 150

chains possessing higher mobility. Additionally, reducing fibre

length makes fibres act as nucleating agents in NPFCs, improving
Epoxy

crystallinity [199e201]. Similarly, polymer chain mobility can

change melting point and glass transition temperature. The higher
chain mobility obtained after multiple recycling cycles reduces
Graphene nanoplatelets (1 wt%)

electrolyte melamine (20 wt%)

phosphonate ester (0.94 wt%)
polyphosphate þ expandable

cationic chitosan and anionic

melting point and glass transition temperature. When natural fibre

phytic acid, as well as the
Biobased electrolytes, i.e.,

experience multiple high-temperature reprocessing, plasticisers-

flame-retardant cationic

like materials extracted from natural fibres can act as slipper

An aqueous organic

Boric acid (30 wt%)

agent among polymer chains which increases chain mobility.

graphite (5 wt%)

However, the restriction of chain mobility due to increased cross-

Ammonium

linked networks and the charring effect associated with fibre

degradation can result in opposite trends in these temperatures.
Either fibre degradation or matrix depolymerisation can enhance
the degradation temperature of NPFCs due to the enhancement of
crystallinity [190,202e204]. NFPCs typically show high moisture/
compared to matrix)

water absorption levels during their service life. As discussed

earlier, reprocessing NFPCs can improve fibre dispersion and
Bamboo (22 wt%)

Ramie (~52 wt%)

reduce fibre length. As a result, the effective surface between in-

Jute (1:1 ratio

Jute (40 vol%)

Jute (40 vol%)

dividual fibres and matrix increases. The matrix can act as a pro-
tective layer for the fibre surface, reducing moisture/water
absorption. During the reprocessing of NFPCs, there is a chance of
degradation of hydrophilic components (e.g., hemicellulose),
21
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Fig. 14. The effect of multiple recycling/reprocessing on various properties of NFPCs.

making reprocessed NFPCs more hydrophobic and resistant to reprocessing times, the oxidation level can promote the efficiency
water. The natural reinforcements (e.g., rice hulk) are sometimes of compatibilisers and interfacial interaction, resulting in improved
inherently equipped with water resistance content such as silica, mechanical performance after reprocessing of NFPCs [210e212].
which can contribute to water resistance behaviour. However, During NFPC fabrication or reprocessing, polymer matrices and
fibrillation of natural fibre-posing fibril structures can promote high reinforcement content require high temperature and shear
water/moisture penetration with easing moisture penetration, but forces to guarantee sufficient compounding and a high level of
it also can improve the interfacial adhesion and matrix protective dispersion/distribution of reinforcements. Exposing natural rein-
behaviour [205e207]. Rheological property is the predominant forcement to a high-temperature environment results in natural
factor affecting the processability of NFPCs. NFPCs with insufficient reinforcement degradation and significantly reduces mechanical
melt strength and viscoelastic behaviour will introduce challenges performance. Therefore, various processing additives such as
during repurposing NFPCs using high-shear environments such as plasticisers, antioxidants, and processing aids are utilised to facili-
twin-screw extrusions. Typically, NFPCs contain high content (e.g., tate the compounding stage and avoid early degradation by
>~30 wt%) of reinforcement phase (e.g., natural fibre). High fibre reducing the melt viscosity, inducing shear-thinning, promoting
content can cause internal friction and heat buildup during the melt flow at localised high shear zones, scavenging free radical,
reprocessing. Therefore, there is a chance of matrix and fibre and reducing residential time in the processing units (e.g.,
degradation and early degradation in NFPCs can considerably extruder) [213e215].
reduce melt viscosity. However, other factors, including crosslinked Traditional flame retardants present a challenge when discus-
networks and fibre degradation formation, can increase melt vis- sing the environmental aspects of flame-resistant NFPCs, as they
cosity. Having reprocessed multiple times, the matrices in NFPCs can potentially result in greenwashing and misleading sustain-
experience a degradation phase, and the fibre length becomes short ability claims. While natural fibres indeed offer ecological benefits,
enough to align with the matrix's flow easily. These effects promote including end-of-life disposal options, recyclability, and heightened
the shear-thinning behaviour of NFPCs and viscosity reduction fuel efficiency in lightweight vehicles (contributing to a reduced
[189,201,208,209]. carbon footprint), a significant issue arises with many of the flame
During NFPCs fabrication, the compounding formulations retardants currently employed in NFPCs. These substances often
consist of various components, including matrix, reinforcing phase lack environmental friendliness and have the potential to persist in
(e.g., fibre or powder), processing additives (e.g., thermal stabil- the environment for extended periods, spanning decades.
isers, antioxidants, lubricants, processing aids, plasticisers, and Furthermore, they can accumulate within human and animal or-
chain extenders), compatibilisers/coupling agents, functional ma- ganisms over time, a phenomenon known as bioaccumulation
terials (e.g., flame retardants and nanomaterials). [216,217]. Hence, a pressing and imperative demand exists for
The reprocessing of NFPCs degrades compatibilisers. Therefore, developing sustainable, bio-derived flame retardants tailored for
the thermal stability of compatibilisers can prolong their func- NFPCs. These innovative flame retardants stem from natural sour-
tionalities during multiple recycling cycles. Generally, during initial ces, encompassing animal and plant origins. Materials such as

22
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

chitosan [218], proteins [219], lignin [220], cellulose [221], starch In addition to employing various methods to enhance composite
[222], deoxyribonucleic acid [223], tannins [224], phytic acid [225], fire retardancy, several other factors impact the properties of nat-
oyster shell powder [226], and eggshell [227] are among the ural fibre composites, including the nature of fibres and compos-
components utilised. Introducing these additives into bio- ites, their density, thickness, structure, thermal conductivity, and
composites has yielded materials exhibiting flame-retardant humidity. While NFPCs offer a sustainable and environmentally
behaviour that satisfies various criteria established by diverse sound approach to manufacturing lightweight, energy-efficient
flammability and fire testing protocols. In addition to these func- composites, challenges such as inconsistent fibre quality, interfa-
tionalities, lignocellulose, known as abundantly available biomass cial interaction between fibres and polymer matrices, moisture
on the Earth, can produce a porous network capable of in-situ absorption, and durability pose significant hurdles in achieving
microbial environmental bioremediation through adsorption and high-performance, fire-retardant natural fibre composites.
degradation of PFAS [228]. Moreover, in contrast to conventional Furthermore, biodeterioration challenges natural fibre com-
flame retardants, including halogenated type, phosphorus- posites, particularly in high humidity and elevated temperatures.
containing type, nitrogen-containing type, and metal oxide type, Hence, a variety of strategies can be employed to develop flame-
most of these bio-based alternatives are harnessed from natural retardant natural fibre-reinforced composites:
waste materials, necessitating certain modifications before their
integration into NFPCs due to compatibility issues. From an eco-  Treating or incorporating natural fibres with fire-retardant
nomic standpoint, synthesising these bio-based flame retardants is functional materials or integrating non-flammable fillers, intu-
generally cost-effective and can mitigate biowaste accumulation in mescent inorganic nanomaterials, and coatings to prevent
landfills. As research progresses, adopting sustainable bio-derived ignition and fire.
flame retardants could mark a pivotal step toward enhancing the  Employing materials that can dissipate or absorb substantial
environmental profile of flame-resistant NFPCs, aligning with both amounts of heat when fibres are exposed to fire or ignition.
safety and ecological objectives [229]. The combination of biobased  Utilizing materials that promote charring characteristics or
flame retardant and natural fibre resulted in the fabrication of hybridising fibres with such materials.
flame-resistant high-performance biocomposites and biofabric,
whose applications are limited to communal and military appli- In conclusion, flame-retardant natural fibre-reinforced com-
cations such as military uniforms [230]. posites represent a promising avenue for sustainable and fire-
Reprocessing and multiple recycling of NFPCs consisting of high resistant materials. This research field has demonstrated the po-
content of flame retardants like intumescent ammonium poly- tential to marry the eco-friendly attributes of natural fibres with
phosphate result in the degradation of both matrix and flame re- effective flame-retardant strategies, thus offering a compelling
tardants simultaneously and reduction in fire resistance behaviour. solution for various applications. By developing innovative ap-
Also, flame retardants will tend to migrate from the polymer during proaches to enhance the fire performance of these composites
reprocessing unless a coupling agent is used [231,232]. Similarly, while preserving their mechanical performance, we can contribute
aluminium trihydrate can start decomposition when the temper- to more environmentally friendly materials for the future. As we
ature reaches 200
C. Therefore, during the recycling of NFPCs, navigate the path towards a sustainable society, the development of
including aluminium trihydrate, special consideration should be such composites holds great promise in addressing both ecological
given to the temperature profile selected for the reprocessing stage. concerns and fire safety requirements.
However, other flame retardants, including magnesium dihydrate, As the demand for eco-friendly products continues to rise, the
decabromodiphenyl ethane, red phosphorus, or those based on recyclability and sustainability of NFPCs can be emerged as a key
nitrogen compounds, are more thermal resistant during recycling focus of future research. NFPCs are renewable and biodegradable,
and reprocessing NFPCs [233e236]. 2D nanomaterials, including offering a sustainable alternative to traditional synthetic compos-
nanoclay, graphene, and transition metal dichalcogenides, are ites, presenting opportunities to effectively manage material usage.
another novel class of flame retardants used in NFPCs. These 2D Compared to the traditional synthetic composites, facing several
nanomaterials, known as physical barriers for combustion, possess challenges and limitations during recycling, the innovations in
stacked layers. These stack layers can experience intercalation and NFPCs have been concentrated on enhancing the compatibility
semi-exfoliation during NFPCs fabrication. Subsequently, further between material selection and recyclability, utilizing bio-based
processing during the recycling of NFPCs can lead to full exfoliation polymer matrices, and improving recycling and recovery yields.
of stack layers; therefore, a better barrier effect can be obtained in As this field progresses, the incorporation of these advancements
NFPCs [237e240]. will play a crucial role in transitioning towards a more environ-
mentally responsible and resource-efficient future.
6. Conclusion
CRediT authorship contribution statement
Pursuing a sustainable society requires advancing sustainable
materials derived from natural resources. It has been proven that
Mojtaba Ahmadi: Writing e original draft, Methodology,
the adoption of NFPCs has grown substantially due to their
Investigation, Formal analysis, Data curation. Omid Zabihi: Writing
renewable nature, recyclability, cost-effectiveness, biodegrad-
e original draft, Investigation, Formal analysis, Conceptualization.
ability, and broad accessibility. However, in contrast to fibres such
Zahra Komeily Nia: Writing e original draft, Data curation. Vishnu
as glass or carbon, natural fibres are more susceptible to fire,
Unnikrishnan: Writing e original draft, Data curation. Colin J.
making composites or fibres more vulnerable to flammability.
Barrow: Writing e review & editing, Supervision. Minoo Naebe:
NFPCs experience a reduction in their mechanical properties
Writing e review & editing, Supervision, Resources, Funding
when exposed to fire or intense heat, depending on the environ-
acquisition, Conceptualization.
mental conditions. Strategies such as impregnation or functionali-
sation with fire retardant materials, non-flammable polymer
matrices or resins and coating composites with heat-resistant Declaration of competing interest
substances have proven effective in enhancing natural fibre com-
posites' mechanical properties and flame retardancy. The authors have no conflict of interest to declare.
23
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

Acknowledgement [27] K. Benzarti, X. Colin, Understanding the Durability of Advanced Fibre-

Reinforced Polymer (FRP) Composites for Structural Applications,
Advanced Fibre-Reinforced Polymer (FRP) Composites for Structural Appli-
The authors acknowledge Dr Alper Kiziltak and Dr Patrick cations, Elsevier, 2013, pp. 361e439.
Blanchard from Research and Innovation Centre, Ford Motor [28] A. Mouritz, Durability of Composites Exposed to Elevated Temperature and
Company for supporting this project. Fire, Durability of Composites for Civil Structural Applications, Elsevier, 2007,
pp. 98e125.
[29] A. Basnayake, J.H. Medina, L. Vandi, M. Heitzmann, Literature Review of
Natural Fibre Composite Fire Properties, 2018.
References [30] A.P. Mouritz, A.G. Gibson, Fire Properties of Polymer Composite Materials,
Springer Science & Business Media, 2007.
[1] S. Singh, M. Uddin, C. Prakash, Introduction, history, and origin of composite [31] B. Schartel, T.R. Hull, Development of fire-retarded materialsd
materials, Fabrication and Machining of Advanced Materials and Composites, interpretation of cone calorimeter data, Fire and Materials, Int. J. 31 (5)
CRC Press, pp. 1-18. (2007) 327e354.
[2] R. Das, C. Bhattacharjee, Chapter 4 - green composites, the next-generation [32] M.L. Galaska, A.R. Horrocks, A.B. Morgan, Flammability of natural plant and
sustainable composite materials: specific features and applications, in: animal fibers: a heat release survey, Fire Mater. 41 (3) (2017) 275e288.
T. Altalhi, Inamuddin (Eds.), Green Sustainable Process for Chemical and [33] R. Turco, I. Corrado, D. Zannini, L. Gargiulo, M. Di Serio, C. Pezzella,
Environmental Engineering and Science, Elsevier, 2022, pp. 55e70. G. Santagata, Upgrading cardoon biomass into Polyhydroxybutyrate based
[3] R. Alagirusamy, Flexible Towpregs and Their Thermoplastic Composites, CRC blends: a holistic approach for the synthesis of biopolymers and additives,
Press, 2022. Bioresour. Technol. 363 (2022) 127954.
[4] S.J. Christian, 8 - natural fibre-reinforced noncementitious composites (bio- [34] W. Song, M. Wu, Y. He, Y. Wu, W. Qu, The evolution of intumescent char
composites), in: K.A. Harries, B. Sharma (Eds.), Nonconventional and Vernacular in flame-retardant coatings based on amino resin, Coatings 11 (6) (2021)
Construction Materials, second ed., Woodhead Publishing, 2020, pp. 169e187. 709.
[5] K. Gautam, R. Vishvakarma, P. Sharma, A. Singh, V. Kumar Gaur, S. Varjani, [35] B.J. Meacham, Fire performance and regulatory considerations with modern
J. Kumar Srivastava, Production of biopolymers from food waste: constrains methods of construction, Buildings and Cities 3 (1) (2022).
and perspectives, Bioresour. Technol. 361 (2022) 127650. [36] M.M. Hirschler, Noncombustibility: testing and regulatory requirements, Fire
[6] M. Bar, R. Alagirusamy, A. Das, Flame retardant polymer composites, Fibers Mater. 47 (2023) 182e198.
Polym. 16 (4) (2015) 705e717. [37] R.E. Lyon, M.L. Janssens, Polymer Flammability, 2005.
[7] L. Mohammed, M.N. Ansari, G. Pua, M. Jawaid, M.S. Islam, A review on natural [38] M.L. Janssens, 10 - challenges in fire testing: a tester's viewpoint, in:
fiber reinforced polymer composite and its applications, International Jour- A.R. Horrocks, D. Price (Eds.), Advances in Fire Retardant Materials, Wood-
nal of Polymer Science 2015 (2015). head Publishing, 2008, pp. 233e254.
[8] N. Kim, S. Dutta, D. Bhattacharyya, A review of flammability of natural fibre [39] V. Kodur, S. Venkatachari, V.A. Matsagar, S.B. Singh, Test methods for char-
reinforced polymeric composites, Compos. Sci. Technol. 162 (2018) 64e78. acterizing the properties of fiber-reinforced polymer composites at elevated
[9] K.L. Pickering, M.A. Efendy, T.M. Le, A review of recent developments in temperatures, Polymers 14 (9) (2022) 1734.
natural fibre composites and their mechanical performance, Compos. Appl. €
[40] M. Janssens, B. Ostman, Reaction to Fire Performance, Fire Safe Use of Wood
Sci. Manuf. 83 (2016) 98e112. in Buildings, CRC Press, 2022, pp. 153e192.
[10] H. Geng, T. Xu, G. Li, Combustion behavior and thermal degradation of [41] U. Sorathia, Materials in Military Applications, Handbook of Building Mate-
bamboo fiber reinforced polyethylene composites, Polym. Compos. 36 (9) rials for Fire Protection, 2004.
(2015) 1574e1581. [42] A.B. Strong, Fundamentals of Composites Manufacturing: Materials, Methods
[11] X. Zhao, R.K. Li, S.L. Bai, Flame retardant and mechanical properties of natural and Applications, Society of Manufacturing Engineers, 2008.
fiber-reinforced polymer composites containing diverse fire retardants, [43] UL (Underwriters Laboratories), UL 94 Standard for Safety of Flammability of
Compos. Appl. Sci. Manuf. 107 (2018) 625e633. Plastic Materials for Parts in Devices and Appliances Testing, 2020.
[12] A.T.M.F. Ahmed, M.Z. Islam, M.S. Mahmud, M.E. Sarker, M.R. Islam, Hemp as a [44] V. Apte (Ed.), Flammability Testing of Materials Used in Construction,
potential raw material toward a sustainable world: a review, Heliyon 8 (1) Transport, and Mining, Woodhead Publishing, 2021.
(2022) e08753. [45] ISO (International Organization for Standardization), Reaction-to-fire tests -
[13] S. Chapple, R. Anandjiwala, Flammability of natural fiber-reinforced com- heat release, smoke production and mass loss rate - Part 1: heat release rate
posites and strategies for fire retardancy: a review, J. Thermoplast. Compos. (cone calorimeter method), ISO 5660-1 (2015) 1-50.
Mater. 23 (6) (2010) 871e893. [46] ASTM International, Standard Test Method for Measuring the Minimum
[14] P. Peças, H. Carvalho, H. Salman, M. Leite, Natural fibre composites and their Oxygen Concentration to Support Candle-like Combustion of Plastics (Oxy-
applications: a review, Journal of Composites Science 2 (4) (2018) 66. gen Index), ASTM D2863-19, 2019.
[15] N.K. Kim, S. Dutta, D. Bhattacharyya, A review of flammability of natural fibre [47] R.E. Lyon, R.N. Walters, Pyrolysis combustion flow calorimetry, J. Anal. Appl.
reinforced polymeric composites, Compos. Sci. Technol. 162 (2018) 64e78. Pyrol. 71 (1) (2004) 27e46.
[16] R.M. Kozłowski, M. Muzyczek, 10 - improving the flame retardancy of natural [48] M.L. Janssens, 2 - fundamental measurement techniques, in: V. Apte (Ed.),
fibres, in: R.M. Kozłowski, M. Mackiewicz-Talarczyk (Eds.), Handbook of Flammability Testing of Materials Used in Construction, Transport and
Natural Fibres, second ed., Woodhead Publishing, 2020, pp. 355e391. Mining, second ed., Woodhead Publishing, 2022, pp. 23e61.
[17] A. Blum, B.N. Ames, Flame-retardant additives as possible cancer hazards, [49] B. Sundstro €m, 8 - cables, in: V. Apte (Ed.), Flammability Testing of Materials
Science 195 (4273) (1977) 17e23. Used in Construction, Transport and Mining, second ed., Woodhead Pub-
[18] D. Boryo, R. Aiyedipe, A. Ezeribe, H. Biri, Effects of urea. Borax and ammo- lishing, 2022, pp. 193e209.
nium chloride on flame retarding properties of cellulosic ceiling board, [50] P.M. Doley, A.C.Y. Yuen, I. Kabir, L. Liu, C. Wang, T.B.Y. Chen, G.H. Yeoh,
Chem. Process Eng. Res. 14 (2013) 1e6. Thermal hazard and smoke toxicity assessment of building polymers
[19] S. Veerappagounder, G. Nalankilli, O. Shanmugasundaram, Study on prop- incorporating TGA and FTIR, Integrated Cone Calorimeter Arrangement, Fire
erties of cotton fabric incorporated with diammonium phosphate flame 5 (5) (2022) 139.
retardant through cyclodextrin and 1, 2, 3, 4-butane tetracarboxylic acid [51] R.A. Pethrick, TEST METHODS, Characterization and Analysis of Polymers,
binding system, J. Ind. Textil. 45 (6) (2016) 1204e1220. 2008, p. 31.
[20] S. Basak, K. Samanta, S. Chattopadhyay, S. Das, R. Narkar, C. Dsouza, [52] M. Rajaei, N.K. Kim, D. Bhattacharyya, Effects of heat-induced damage on
A. Shaikh, Flame Retardant and Antimicrobial Ligno-Cellulosic Fabric Using impact performance of epoxy laminates with glass and flax fibres, Compos.
Sodium Metasilicate Nonahydrate, 2014. Struct. 185 (2018) 515e523.
[21] R. Kumar, J. Gunjal, S. Chauhan, Effect of borax-boric acid and ammonium [53] S. Fatima, A.R. Mohanty, Acoustical and fire-retardant properties of jute
polyphosphate on flame retardancy of natural fiber polyethylene compos- composite materials, Appl. Acoust. 72 (2) (2011) 108e114.
ites, Maderas Cienc. Tecnol. 24 (2022). [54] B.C. Hagen, A.K. Meyer, From smoldering to flaming fire: different modes of
[22] J. Lazko, N. Landercy, F. Laoutid, L. Dangreau, M.H. Huguet, O. Talon, Flame transition, Fire Saf. J. 121 (2021) 103292.
retardant treatments of insulating agro-materials from flax short fibres, [55] K. Yoganandam, B. NagarajaGanesh, P. Ganeshan, K. Raja, Thermogravimetric
Polym. Degrad. Stabil. 98 (5) (2013) 1043e1051. analysis of Calotropis procera fibers and their influence on the thermal
[23] J. Teslík, M. Hos t a
0
lkov
a, N. Vavrínova
, Ignitability small attack flame fire test conductivity and flammability studies of polymer composites, Mater. Res.
of gypsum composite reinforced with natural fibres, International Review of Express 6 (10) (2019) 105341.
Applied Sciences and Engineering 10 (1) (2019) 57e61. [56] M.D.A.R. Dayan, M.D.M. Rahman, J. Ferdush, M.A. Kaysar, M.D.M. Uddin, Ef-
[24] A.F. Robertson, Fire Standards and Safety: A Symposium Presented at Na- fect of harvesting time on the fiber yield and characterization of jute fiber,
tional Bureau of Standards, U.S. Government Printing Office1977, Gaithers- J. Nat. Fibers 19 (15) (2022) 12434e12445.
burg, Md, 5-6 April 1976. [57] S.M.K. Thiagamani, R. Nagarajan, M. Jawaid, V. Anumakonda, S. Siengchin,
[25] R. Kozlowski, M. Helwig, Fire retardancy of lignocellulosic composites. 9th Utilization of chemically treated municipal solid waste (spent coffee bean
Annual Conf Recent Advances in Flame Retardancy of Polymeric Materials, powder) as reinforcement in cellulose matrix for packaging applications,
Business Communications Co, Norwalk, USA, 1998. Waste Manag. 69 (2017) 445e454.
[26] Y.K. Kim, V. Chalivendra, Natural Fibre Composites (NFCs) for Construction [58] S. Sethupathy, G. Murillo Morales, L. Gao, H. Wang, B. Yang, J. Jiang, J. Sun,
and Automotive Industries, Handbook of Natural Fibres, Elsevier, 2020, D. Zhu, Lignin valorization: status, challenges and opportunities, Bioresour.
pp. 469e498. Technol. 347 (2022) 126696.

24
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

[59] A. Elsabbagh, T. Attia, A. Ramzy, L. Steuernagel, G. Ziegmann, Towards se- [87] J. Zhan, J. Wang, J. Lin, G. Zhao, S. Ji, X. Li, J. Li, G. Wang, L. Chen, Y. Guan,
lection chart of flame retardants for natural fibre reinforced polypropylene H. Naceur, Flame-retardant, thermal and mechanical properties of PLA/ramie
composites, Compos. B Eng. 141 (2018) 1e8. fiber composites, Polym. Compos. 43 (7) (2022) 4244e4254.
[60] A.U.R. Shah, M. Prabhakar, J.-I. Song, Current advances in the fire retardancy [88] G.S. Balan, R. Balasundaram, K. Chellamuthu, S.N. Gopan, S. Dinesh,
of natural fiber and bio-based compositeseA review, International journal of V. Vijayan, T. Sathish, S. Rajkumar, Flame resistance characteristics of woven
precision engineering and manufacturing-green technology 4 (2) (2017) jute fiber reinforced fly ash filled polymer composite, J. Nanomater. 2022
247e262. (2022) 9704980.
[61] R. Kozłowski, M. Władyka-Przybylak, Flammability and fire resistance of [89] V. Chalapathi, U.R.S. Atta, J.-i. Song, Effect of synthesized chitosan flame
composites reinforced by natural fibers, Polym. Adv. Technol. 19 (6) (2008) retardant on flammability, thermal, and mechanical properties of vinyl ester/
446e453. bamboo nonwoven fiber composites, Research Square 1 (2021) 1e25.
[62] V. Sekar, M.H. Fouladi, S.N. Namasivayam, S. Sivanesan, Additive [90] W. Du, X. Ge, H. Huang, T. Zhang, Z. Zhang, X. Shang, Fabrication of high
manufacturing: a novel method for developing an acoustic panel made of transparent, mechanical strong, and flame retardant waterborne poly-
natural fiber-reinforced composites with enhanced mechanical and acous- urethane composites by incorporating phosphorus-silicon functionalized
tical properties, J. Eng. 2019 (2019). cellulose nanocrystals, J. Appl. Polym. Sci. 139 (3) (2022) 51496.
[63] T. Sathishkumar, P. Navaneethakrishnan, S. Shankar, R. Rajasekar, N. Rajini, [91] Y.-H. Guan, W. Liao, Z.-Z. Xu, M.-J. Chen, J.-Q. Huang, Y.-Z. Wang, Improve-
Characterization of natural fiber and compositeseA review, J. Reinforc. Plast. ment of the flame retardancy of wood-fibre/polypropylene composites with
Compos. 32 (19) (2013) 1457e1476. ideal mechanical properties by a novel intumescent flame retardant system,
[64] I. Mukhtar, Z. Leman, M.R. Ishak, E.S. Zainudin, Sugar palm fibre and its RSC Adv. 5 (74) (2015) 59865e59873.
composites: a review of recent developments, Bioresources 11 (4) (2016) [92] Y.-H. Guan, J.-Q. Huang, J.-C. Yang, Z.-B. Shao, Y.-Z. Wang, An effective way to
10756e10782. flame-retard biocomposite with ethanolamine modified ammonium poly-
[65] S. Chukwunwike, I.E. Ike-Eze, A. Vs, KJ Okafor Flammability properties of phosphate and its flame retardant mechanisms, Ind. Eng. Chem. Res. 54 (13)
flame retarded natural fibre reinforced polymer composites: an overview, (2015) 3524e3531.
J. Mater. Environ. Sci. 10 (7) (2019) 647e656. [93] M.J. John, Biobased alginate treatments on flax fibre reinforced PLA and
[66] B.M. Pejic, M.M. Kostic, P.D. Skundric, J.Z. Praskalo, The effects of hemi- PHBV composites, Current Research in Green and Sustainable Chemistry 5
celluloses and lignin removal on water uptake behavior of hemp fibers, (2022) 100319.
Bioresour. Technol. 99 (15) (2008) 7152e7159. [94] L. Liu, B. Shi, A. Zhang, Y. Xue, J. Zhang, J. Dai, M. Hassanpour, L.-C. Tang,
[67] A.L. Mohamed, A.G. Hassabo, Flame Retardant of Cellulosic Materials and Y. Shi, P. Song, A polyphosphoramide-grafted lignin enabled thermostable
Their Composites, Flame Retardants, Springer, 2015, pp. 247e314. and fire-retardant polylactide with preserved mechanical properties, Com-
[68] A.R. Horrocks, D. Price, D. Price, Fire Retardant Materials, woodhead Pub- pos. Appl. Sci. Manuf. 160 (2022) 107028.
lishing, 2001. [95] C. Campana, R. Le ger, R. Sonnier, P. Ienny, L. Ferry, Effect of hygrothermal
[69] D. Ferdous, A. Dalai, S. Bej, R. Thring, Pyrolysis of lignins: experimental and ageing on the mechanical and fire properties of a flame retardant flax fiber/
kinetics studies, Energy Fuels 16 (6) (2002) 1405e1412. epoxy composite, Polymers 14 (19) (2022) 3962.
[70] B. Cagnon, X. Py, A. Guillot, F. Stoeckli, G. Chambat, Contributions of hemi- [96] Y. Yang, L. Haurie, J. Wen, S. Zhang, A. Ollivier, D.-Y. Wang, Effect of oxidized
cellulose, cellulose and lignin to the mass and the porous properties of chars wood flour as functional filler on the mechanical, thermal and flame-
and steam activated carbons from various lignocellulosic precursors, Bio- retardant properties of polylactide biocomposites, Ind. Crop. Prod. 130
resour. Technol. 100 (1) (2009) 292e298. (2019) 301e309.
[71] H.L. Ornaghi, F.G. Ornaghi, R.M. Neves, F. Monticeli, O. Bianchi, Mechanisms [97] R. Kumar, S. Chauhan, Effect of ammonium polyphosphate as synergist with
involved in thermal degradation of lignocellulosic fibers: a survey based on nano silica dioxide on flammability of boron compound pretreated bamboo
chemical composition, Cellulose 27 (9) (2020) 4949e4961. flour-HDPE composite, Fire Saf. J. 133 (2022) 103647.

[72] A. Alvarez, C. Pizarro, R. García, J. Bueno, A. Lavín, Determination of kinetic [98] Z.C. Lule, J. Kim, Surface treatment of lignocellulose biofiller for fabrication of
parameters for biomass combustion, Bioresour. Technol. 216 (2016) 36e43. sustainable polylactic acid biocomposite with high crystallinity and
[73] X. Zhang, R. Huang, Thermal decomposition kinetics of basalt fiber- improved burning antidripping performance, Mater. Today Chem. 23 (2022)
reinforced wood polymer composites, Polymers 12 (10) (2020) 2283. 100741.
[74] F. Yao, Q. Wu, Y. Lei, W. Guo, Y. Xu, Thermal decomposition kinetics of [99] I.C. Nwuzor, J.L. Chukwuneke, C.M. Ewulonu, P.C. Okolie, Fabrication of car-
natural fibers: activation energy with dynamic thermogravimetric analysis, danol thermosetting resin reinforced with cellulose nanofibril/expanded
Polym. Degrad. Stabil. 93 (1) (2008) 90e98. graphite nano-biocomposites, Ind. Crop. Prod. 187 (2022) 115392.
[75] F. Yao, Q. Wu, D. Zhou, Thermal decomposition of natural fibers: global ki- [100] Y. Tao, P. Li, L. Cai, S.Q. Shi, Flammability and mechanical properties of
netic modeling with nonisothermal thermogravimetric analysis, J. Appl. composites fabricated with CaCO3-filled pine flakes and Phenol Formalde-
Polym. Sci. 114 (2) (2009) 834e842. hyde resin, Compos. B Eng. 167 (2019) 1e6.
[76] F. Xu, L. Zhong, Y. Xu, C. Zhang, F. Zhang, G. Zhang, Highly efficient flame- [101] A. Suwanniroj, N. Suppakarn, Influence of glycidyl methacrylate grafted poly
retardant and soft cotton fabric prepared by a novel reactive flame retar- (butylene succinate) (PBS-g-GMA) on flame retardancy and mechanical
dant, Cellulose 26 (2019) 4225e4240. properties of water hyacinth fiber/ammonium polyphosphate/poly
[77] Y.-L. Lam, C.-W. Kan, C.-W.M. Yuen, Developments in functional finishing of (butylene succinate) composites, J. Appl. Polym. Sci. 139 (43) (2022) e53063.
cotton fibresewrinkle-resistant, flame-retardant and antimicrobial treat- [102] A.A. Borazan, D. Gokdai, Pine cone and boron compounds effect as rein-
ments, Textil. Prog. 44 (3e4) (2012) 175e249. forcement on mechanical and flammability properties of polyester com-
[78] C. Liu, Z. Tan, H.M. Li, Z.W. Xie, J.P. Peng, M.L. Liang, J.W. Guo, Research posites, Open Chem. 16 (1) (2018) 427e436.
Progress in Cellulose Extraction, Modification and Application, Materials [103] F. Gapsari, A. Purnowidodo, P.H. Setyarini, S. Suteja, Z. Abidin, S.M. Rangappa,
Science Forum, Trans Tech Publ, 2016, pp. 1194e1200. S. Siengchin, Flammability and mechanical properties of Timoho fiber-
[79] S. Shahidi, Novel method for ultraviolet protection and flame retardancy of reinforced polyester composite combined with iron powder filler, J. Mater.
cotton fabrics by low-temperature plasma, Cellulose 21 (1) (2014) Res. Technol. 21 (2022) 212e219.
757e768. [104] S. Ehsanimehr, R. Sonnier, P. Najafi, F. Ducos, M. Badawi, K. Formela,
[80] S. Peter, N. Lyczko, D. Gopakumar, H.J. Maria, A. Nzihou, S. Thomas, Nano- M.R. Saeb, H. Vahabi, Layer-by-layer polymer deposited fabrics with superior
cellulose and its derivative materials for energy and environmental appli- flame retardancy and electrical conductivity, React. Funct. Polym. 173 (2022)
cations, J. Mater. Sci. 57 (13) (2022) 6835e6880. 105221.
[81] R.M. Kozlowski, M. Muzyczek, J. Walentowska, Chapter 23 - flame retardancy ment, B. Ameduri, R. Sonnier, B. Otazaghine, Flame
[105] J. Taibi, S. Rouif, J.-L. Cle
and protection against biodeterioration of natural fibers: state-of-art and retardancy of flax fibers by pre-irradiation grafting of a phosphonate
future prospects, in: C.D. Papaspyrides, P. Kiliaris (Eds.), Polymer Green monomer, Ind. Crop. Prod. 176 (2022) 114334.
Flame Retardants, Elsevier, Amsterdam, 2014, pp. 801e836. [106] C.R.S. de Oliveira, M.A. Batistella, S.M.d.A. Guelli Ulson de Souza, A.A. Ulson
[82] C.Q. Yang, 7 - flame resistant cotton, in: F.S. Kilinc (Ed.), Handbook of Fire de Souza, Functionalization of cellulosic fibers with a kaolinite-TiO2 nano-
Resistant Textiles, Woodhead Publishing, 2013, pp. 177e220. hybrid composite via a solvothermal process for flame retardant applica-
[83] N. Cinausero, A. Fina, J. Hao, S. Nazare, E. Kandore, J. Staggs, Y.C. Wang, tions, Carbohydr. Polym. 266 (2021) 118108.
S. Duquesne, R. Hicklin, P. Wakelyn, Fire Retardancy of Polymers: New [107] P. Fei, Z. Guo, C. Ye, Z. Teng, Q. Chen, G. Zhang, Y. Zhuang, W. Lai, H. Xiong,
Strategies and Mechanisms, Royal Society of Chemistry, 2008. J. Cai, The enhancement of the flame retardance of bamboo fibre/HDPE
[84] S. Gaan, V. Salimova, P. Rupper, A. Ritter, H. Schmid, 5 - flame retardant composites: cerium doped H2Ti2O5$H2O nanotubes effects, Construct. Build.
functional textiles, in: N. Pan, G. Sun (Eds.), Functional Textiles for Improved Mater. 201 (2019) 728e735.
Performance, Protection and Health, Woodhead Publishing, 2011, [108] R. Hajj, R. El Hage, R. Sonnier, B. Otazaghine, B. Gallard, S. Rouif, M. Nakhl, J.-
pp. 98e130. M. Lopez-Cuesta, Grafting of phosphorus flame retardants on flax fabrics:
[85] G.N. Thyssen, B.D. Condon, D.J. Hinchliffe, L. Zeng, M. Naoumkina, comparison between two routes, Polym. Degrad. Stabil. 147 (2018) 25e34.
J.N. Jenkins, J.C. McCarty, R. Sui, C. Madison, P. Li, D.D. Fang, Flame resistant [109] S.-Q. Li, R.-C. Tang, C.-B. Yu, Flame retardant treatment of jute fabric with
cotton lines generated by synergistic epistasis in a MAGIC population, PLoS chitosan and sodium alginate, Polym. Degrad. Stabil. 196 (2022) 109826.
One 18 (1) (2023) e0278696. [110] R.D.S.G. Campilho, Natural Fiber Composites, CRC Press, 2015.
[86] Q. Niu, X. Yue, W. Cao, Z. Guo, Z. Fang, P. Chen, J. Li, Interfacial silicon- [111] Z. Zheng, Y. Xia, C. Liao, Y. Liu, W. Chai, E. Niu, Z. Hu, Fabrication of starch-
nitrogen aerogel raise flame retardancy of bamboo fiber reinforced poly- based multi-source integrated halogen-free flame retardant in improving
lactic acid composites, Int. J. Biol. Macromol. 222 (2022) 2697e2708. the fire safety of polypropylene, J. Polym. Res. 28 (11) (2021) 445.

25
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

[112] V. Schenk, K. Labastie, M. Destarac, P. Olivier, M. Guerre, Vitrimer compos- [138] A.G. Gibson, P.N.H. Wright, Y.S. Wu, A.P. Mouritz, Z. Mathys, C.P. Gardiner,
ites: current status and future challenges, Materials Advances 3 (22) (2022) Modelling residual mechanical properties of polymer composites after fire,
8012e8029. Plast., Rubber Compos. 32 (2) (2003) 81e90.
[113] M. Barczewski, K. Sałasin  ska, W. Ras, A. Hejna, S. Michałowski, P. Kosmela, [139] C.L. Beyler, M.M. Hirschler, Thermal decomposition of polymers, SFPE
J. Anisko, A. Boczkowska, M. Szostak, The effect of hybridization of fire handbook of fire protection engineering 2 (7) (2002) 111e131.
retarded epoxy/flax-cotton fiber laminates by expanded vermiculite: [140] A.I. Bartlett, R.M. Hadden, L.A. Bisby, A review of factors affecting the burning
structure-property relationship study, Advanced Industrial and Engineering behaviour of wood for application to tall timber construction, Fire Technol.
Polymer Research 6 (2023) 181e194. 55 (1) (2019) 1e49.
[114] S. Gairola, S. Sinha, I. Singh, Novel millet husk crop-residue based thermo- [141] C. Di Blasi, Modeling chemical and physical processes of wood and biomass
plastic composites: waste to value creation, Ind. Crop. Prod. 182 (2022) pyrolysis, Prog. Energy Combust. Sci. 34 (1) (2008) 47e90.
114891. [142] A.L. Sullivan, R. Ball, Thermal decomposition and combustion chemistry of
[115] C. Havis, G. Peterson, L. Fletcher, Predicting the thermal conductivity and cellulosic biomass, Atmos. Environ. 47 (2012) 133e141.
temperature distribution in aligned fiber composites, J. Thermophys. Heat [143] L. Magunga, M. Mohapi, A. Kaleni, S. Magagula, M.J. Mochane, M.T. Motloung,
Tran. 3 (4) (1989) 416e422. Bioplastics and Biocomposites in Flame-Retardant Applications, Handbook of
[116] S. Ray, R.P. Cooney, Thermal Degradation of Polymer and Polymer Com- Bioplastics and Biocomposites Engineering Applications, 2023, pp. 539e573.
posites, Handbook of Environmental Degradation of Materials, Elsevier, [144] A. Mouritz, C. Gardiner, Z. Mathys, C. Townsend, Post-fire properties of
2018, pp. 185e206. composites burnt by cone calorimetry and large-scale fire testing, in: Pro-
[117] A. Sayyidmousavi, H. Bougherara, S. Falahatgar, Z. Fawaz, Prediction of the ceeding of the ICCM13, Beijing, China, 2001.
effective thermal conductivity of fiber reinforced composites using a [145] A.P. Mouritz, Z. Mathys, Mechanical properties of fire-damaged glass-rein-
micromechanical approach, Journal of Mechanics 35 (2) (2019) 179e185. forced phenolic composites, Fire Mater. 24 (2) (2000) 67e75.
[118] J.D. Farmer, E.E. Covert, Thermal conductivity of a thermosetting advanced [146] A.P. Mouritz, Z. Mathys, Post-fire mechanical properties of marine polymer
composite during its cure, J. Thermophys. Heat Tran. 10 (3) (1996) 467e475. composites, Compos. Struct. 47 (1) (1999) 643e653.
[119] H. Yu, A. Nonn, S. Schneiders, D. Heider, S.G. Advani, An approach to enhance [147] N.P.G. Suardana, M.S. Ku, J.K. Lim, Effects of diammonium phosphate on the
through-thickness thermal conductivity of polymeric fiber composites, Int. J. flammability and mechanical properties of bio-composites, Mater. Des. 32
Heat Mass Tran. 59 (2013) 20e28. (4) (2011) 1990e1999.
[120] S.D. Sharma, S. Puggal, R. Sharma, N. Singh, Effect of fiber orientation on heat [148] L.A. Lowden, T.R. Hull, Flammability behaviour of wood and a review of the
transfer for frp composite, International Journal of Mechanical Engineering methods for its reduction, Fire Science Reviews 2 (1) (2013) 4.
and Robotics Research 4 (2) (2015) 91. [149] T.D. Hapuarachchi, T. Peijs, Multiwalled carbon nanotubes and sepiolite
[121] B.S. Keerthi Gowda, K. Naresh, S. Ilangovan, M.R. Sanjay, S. Siengchin, Effect nanoclays as flame retardants for polylactide and its natural fibre reinforced
of fiber volume fraction on mechanical and fire resistance properties of composites, Compos. Appl. Sci. Manuf. 41 (8) (2010) 954e963.
basalt/polyester and pineapple/polyester composites, J. Nat. Fibers 19 (13) [150] P. Khalili, B. Blinzler, R. Kadar, R. Bisschop, M. Fo €rsth, P. Blomqvist, Flam-
(2022) 6074e6088. mability, smoke, mechanical behaviours and morphology of flame retarded
[122] M. Helwig, D. Paukszta, Flammability of composites based on polypropylene natural fibre/elium® composite, Materials 12 (17) (2019) 2648.
and flax fibers, molecular crystals and liquid crystals science and technology. [151] A. El-Sabbagh, L. Steuernagel, D. Meiners, G. Ziegmann, O. Toepfer, Optimi-
Section A, Mol. Cryst. Liq. Cryst. 354 (1) (2000) 373e380. zation of flame retardant content with respect to mechanical properties of
[123] V. Alvarez, E. Rodriguez, A. Va zquez, Thermaldegradation and decomposition natural fiber polymer composites: case study of polypropylene/flax/
of jute/vinylester composites, J. Therm. Anal. Calorim. 85 (2) (2006) aluminum trihydroxide, Polym. Compos. 37 (11) (2016) 3310e3325.
383e389. [152] Y. Zhu, Z. Yu, J. Zhu, Y. Zhang, X. Ren, F. Jiang, Developing flame-retardant
[124] T. Singh, B. Gangil, L. Ranakoti, A. Joshi, Effect of silica nanoparticles on lignocellulosic nanofibrils through reactive deep eutectic solvent treatment
physical, mechanical, and wear properties of natural fiber reinforced poly- for thermal insulation, Chem. Eng. J. 445 (2022) 136748.
mer composites, Polym. Compos. 42 (5) (2021) 2396e2407. [153] A.I. Osman, M. Farghali, I. Ihara, A.M. Elgarahy, A. Ayyad, N. Mehta, K.H. Ng,
[125] H. Canıtez, A.N. Yüksel Yılmaz, A. Çelik Bedelog lu, The effect of silicon di- E.M. Abd El-Monaem, A.S. Eltaweil, M. Hosny, S.M. Hamed, S. Fawzy, P.-
oxide and zinc borate on the flame retardancy, thermal and mechanical S. Yap, D.W. Rooney, Materials, fuels, upgrading, economy, and life cycle
properties of jute/epoxy hybrid composite, J. Nat. Fibers 20 (1) (2023) assessment of the pyrolysis of algal and lignocellulosic biomass: a review,
2131683. Environ. Chem. Lett. 21 (2023) 1419e1476.
[126] K.R. Sumesh, K. Kanthavel, S. Vivek, Mechanical/thermal/vibrational prop- [154] A. Satdive, S. Tayde, A. Chatterjee, Flammability properties of the bio-
erties of sisal, banana and coir hybrid natural composites by the addition of nanocomposites reinforced with fire retardant filler, in: C. Muthukumar,
bio synthesized aluminium oxide nano powder, Mater. Res. Express 6 (4) S.M.K. Thiagamani, S. Krishnasamy, R. Nagarajan, S. Siengchin (Eds.), Polymer
(2019) 045318. Based Bio-Nanocomposites: Properties, Durability and Applications, Springer
[127] C.A. Arenas-Cha vez, L.M. de Hollanda, A.A. Arce-Esquivel, A. Alvarez-Risco, Singapore, Singapore, 2022, pp. 79e80.
S. Del-Aguila-Arcentales, J.A. Y ~ ez, C. Vera-Gonzales, Antibacterial and
an [155] P. Khalili, X. Liu, K.Y. Tshai, C. Rudd, X. Yi, I. Kong, Development of fire
antifungal activity of functionalized cotton fabric with nanocomposite based retardancy of natural fiber composite encouraged by a synergy between zinc
on silver nanoparticles and carboxymethyl chitosan, Processes 10 (6) (2022) borate and ammonium polyphosphate, Compos. B Eng. 159 (2019) 165e172.
1088. [156] A. Satdive, S. Tayde, A. Chatterjee, Flammability properties of the bio-
[128] A. Saravanan, P. Thirumurugan, S. Rajeshkannan, S. Sridhar, Effect of corn cob nanocomposites reinforced with fire retardant filler, in: C. Muthukumar,
carbon quantum dots and areca husk microfiber on EMI shielding effec- S.M.K. Thiagamani, S. Krishnasamy, R. Nagarajan, S. Siengchin (Eds.), Polymer
tiveness of flexible PVA thin film at 8e20GHz frequency bands, Biomass Based Bio-Nanocomposites: Properties, Durability and Applications, Springer
Conversion and Biorefinery 14 (2023) 18827e18834. Singapore, Singapore, 2022, pp. 69e86.
[129] A. Subasinghe, R. Das, D. Bhattacharyya, Study of thermal, flammability and [157] M. Jalalah, S. Zulfiqar, A. Afzal, Z. Khaliq, M.B. Qadir, A. Abid, M. Faisal,
mechanical properties of intumescent flame retardant PP/kenaf nano- M. Alsaiari, M. Irfan, F.A. Harraz, Microencapsulation based fire retardant
composites, Int. J. Soc. Netw. Min. 7 (3) (2016) 202e220. eco-friendly jute composite, Polym. Polym. Compos. 31 (2023)
[130] Y. Suo, W. Gao, Z. Chen, Y. Yu, T. Chen, C. Li, Q. Zhang, J. Jiang, Surface 09673911221147702.
modification of cellulose nanocrystal and its applications in flame retardant [158] C. Thiyagu, U. NarendraKumar, Effect of ammonium polyphosphate on fire-
epoxy resin, J. Appl. Polym. Sci. 139 (28) (2022) e52617. retardant, mechanical, and vibrational analysis of epoxy/glass/ramie hybrid
[131] J. Zhan, G. Wang, J. Li, Y. Guan, G. Zhao, H. Naceur, D. Coutellier, J. Lin, Effect composite, Polym. Compos. 44 (1) (2023) 621e631.
of the compatilizer and chemical treatments on the performance of poly(- [159] H. Imoto, Y. Nakao, N. Nishizawa, S. Fujii, Y. Nakamura, K. Naka, Tripodal
lactic acid)/ramie fiber composites, Compos. Commun. 27 (2021) 100843. polyhedral oligomeric silsesquioxanes as a novel class of three-dimensional
[132] T. Mai Nguyen Tran, M.N. Prabhakar, J.-i. Song, Influence of biowaste additive emulsifiers, Polym. J. 47 (9) (2015) 609e615.
and treated short woven flax fibers on the flame retardancy and mechanical [160] S. Araby, B. Philips, Q. Meng, J. Ma, T. Laoui, C.H. Wang, Recent advances in
properties of PP composites, Ind. Crop. Prod. 174 (2021) 114176. carbon-based nanomaterials for flame retardant polymers and composites,
[133] A. Rattanapan, Study on the Rheological Behaviour of Sisal Fibre/HDPE Compos. B Eng. 212 (2021) 108675.
Composites with Flame Retardant, Key Engineering Materials, Trans Tech [161] E. Dias, H. Chalse, S. Mutha, Y. Mundhe, N. Ambhore, A. Kulkarni, A. Mache,
Publ, 2017, pp. 307e312. Review on synthetic/natural fibers polymer composite filled with nanoclay
[134] G. Han, J. Bang, H.-J. Jin, H.W. Kwak, Natural fiber nonwoven preform using and their mechanical performance, Mater. Today: Proc. 77 (2023) 916e925.
cellulose nanocrystal as a green additive, Cellulose 30 (5) (2023) 3013e3025. [162] P. Khalili, K.Y. Tshai, I. Kong, Natural fiber reinforced expandable graphite
[135] K. Majeed, M. Jawaid, A. Hassan, A. Abu Bakar, H.P.S. Abdul Khalil, filled composites: evaluation of the flame retardancy, thermal and me-
A.A. Salema, I. Inuwa, Potential materials for food packaging from nanoclay/ chanical performances, Compos. Appl. Sci. Manuf. 100 (2017) 194e205.
natural fibres filled hybrid composites, Mater. Des. 46 (2013) 391e410 [163] Y. Yang, D.-Y. Wang, L. Haurie, Z. Liu, L. Zhang, Combination of corn pith fiber
(1980-2015). and biobased flame retardant: a novel method toward flame retardancy,
[136] M.-p. Ho, H. Wang, J.-H. Lee, C.-k. Ho, K.-t. Lau, J. Leng, D. Hui, Critical factors thermal stability, and mechanical properties of polylactide, Polymers 13 (10)
on manufacturing processes of natural fibre composites, Compos. B Eng. 43 (2021) 1562.
(8) (2012) 3549e3562. [164] L. Zhang, Z. Li, Y.-T. Pan, A.P. Y
an~ ez, S. Hu, X.-Q. Zhang, R. Wang, D.-Y. Wang,
[137] T. Khan, M.T.B. Hameed Sultan, A.H. Ariffin, The challenges of natural fiber in Polydopamine induced natural fiber surface functionalization: a way to-
manufacturing, material selection, and technology application: a review, wards flame retardancy of flax/poly(lactic acid) biocomposites, Compos. B
J. Reinforc. Plast. Compos. 37 (11) (2018) 770e779. Eng. 154 (2018) 56e63.

26
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

[165] I. Ali, N.K. Kim, D. Bhattacharyya, Effects of graphene nanoplatelets on me- [190] M. Bakkal, M.S. Bodur, O.B. Berkalp, S. Yilmaz, The effect of reprocessing on
chanical and fire performance of flax polypropylene composites with intu- the mechanical properties of the waste fabric reinforced composites,
mescent flame retardant, Molecules 26 (13) (2021) 4094. J. Mater. Process. Technol. 212 (11) (2012) 2541e2548.
[166] R. Jeencham, N. Suppakarn, K. Jarukumjorn, Effect of flame retardants on [191] E. Uitterhaegen, J. Parinet, L. Labonne, T. Me rian, S. Ballas, T. Verone
se,
flame retardant, mechanical, and thermal properties of sisal fiber/poly- O. Merah, T. Talou, C.V. Stevens, F. Chabert, P. Evon, Performance, durability
propylene composites, Compos. B Eng. 56 (2014) 249e253. and recycling of thermoplastic biocomposites reinforced with coriander
[167] F. Chu, X. Yu, Y. Hou, X. Mu, L. Song, W. Hu, A facile strategy to simulta- straw, Compos. Appl. Sci. Manuf. 113 (2018) 254e263.
neously improve the mechanical and fire safety properties of ramie fabric- [192] M.D.H. Beg, K.L. Pickering, Reprocessing of wood fibre reinforced poly-
reinforced unsaturated polyester resin composites, Compos. Appl. Sci. propylene composites. Part I: effects on physical and mechanical properties,
Manuf. 115 (2018) 264e273. Compos. Appl. Sci. Manuf. 39 (7) (2008) 1091e1100.
[168] F. Chu, D. Zhang, Y. Hou, S. Qiu, J. Wang, W. Hu, L. Song, Construction of [193] E. Nadali, M. Layeghi, G. Ebrahimi, R. Naghdi, M. Jonoobi, M.M. Khorasani,
hierarchical natural fabric surface structure based on two-dimensional boron Y. Mirbagheri, Effects of multiple extrusions on structure-property perfor-
nitride nanosheets and its application for preparing biobased toughened mance of natural fiber high-density polyethylene biocomposites, Mater. Res.
unsaturated polyester resin composites, ACS Appl. Mater. Interfaces 10 (46) 21 (2018).
(2018) 40168e40179. [194] A. Agüero, M.d.C. Morcillo, L. Quiles-Carrillo, R. Balart, T. Boronat, D. Lascano,
[169] Y. Dou, X. Li, T. Zhang, H. Xu, An intumescent flame-retardant layer with b- S. Torres-Giner, O. Fenollar, Study of the influence of the reprocessing cycles
cyclodextrin as charring agent and its flame retardancy in jute/poly- on the final properties of polylactide pieces obtained by injection molding,
propylene composites, Polym. Bull. 78 (8) (2021) 4281e4296. Polymers 11 (12) (2019) 1908.
[170] B. Guo, T. Zhang, W. Zhang, Y. Dou, Influence of surface flame-retardant layer [195] C. Fonseca-Valero, A. Ochoa-Mendoza, J. Arranz-Andre s, C. Gonzalez-
containing ammonium polyphosphate and expandable graphite on the Sanchez, Mechanical recycling and composition effects on the properties and
performance of jute/polypropylene composites, J. Therm. Anal. Calorim. 135 structure of hardwood cellulose-reinforced high density polyethylene eco-
(4) (2019) 2367e2375. composites, Compos. Appl. Sci. Manuf. 69 (2015) 94e104.
[171] W. Guo, E.N. Kalali, X. Wang, W. Xing, P. Zhang, L. Song, Y. Hu, Processing [196] J.P. Correa-Aguirre, F. Luna-Vera, C. Caicedo, B. Vera-Mondrago  n,
bulk natural bamboo into a strong and flame-retardant composite material, M.A. Hidalgo-Salazar, The effects of reprocessing and fiber treatments on the
Ind. Crop. Prod. 138 (2019) 111478. properties of polypropylene-sugarcane bagasse biocomposites, Polymers 12
[172] P. Khalili, K.Y. Tshai, D. Hui, I. Kong, Synergistic of ammonium polyphosphate (7) (2020) 1440.
and alumina trihydrate as fire retardants for natural fiber reinforced epoxy [197] T. Evens, G.-J. Bex, M. Yigit, J.D. Keyzer, F. Desplentere, A.V. Bael, The influ-
composite, Compos. B Eng. 114 (2017) 101e110. ence of mechanical recycling on properties in injection molding of fiber-
[173] N.K. Kim, D. Bhattacharyya, Development of fire resistant wool polymer reinforced polypropylene, Int. Polym. Process. 34 (4) (2019) 398e407.
composites: mechanical performance and fire simulation with design per- [198] L. Soccalingame, A. Bourmaud, D. Perrin, J.C. Be  ne
zet, A. Bergeret, Reproc-
spectives, Mater. Des. 106 (2016) 391e403. essing of wood flour reinforced polypropylene composites: impact of par-
[174] N.K. Kim, R.J.T. Lin, D. Bhattacharyya, Effects of wool fibres, ammonium ticle size and coupling agent on composite and particle properties, Polym.
polyphosphate and polymer viscosity on the flammability and mechanical Degrad. Stabil. 113 (2015) 72e85.
performance of PP/wool composites, Polym. Degrad. Stabil. 119 (2015) [199] P. Dhar, R.K. M, S.M. Bhasney, P. Bhagabati, A. Kumar, V. Katiyar, Sustainable
167e177. approach for mechanical recycling of poly(lactic acid)/cellulose nanocrystal
[175] A.P. Mouritz, Z. Mathys, Post-fire mechanical properties of glass-reinforced films: investigations on structureeproperty relationship and underlying
polyester composites, Compos. Sci. Technol. 61 (4) (2001) 475e490. mechanism, Ind. Eng. Chem. Res. 57 (43) (2018) 14493e14508.
[176] N.R. Paluvai, S. Mohanty, S.K. Nayak, Studies on thermal degradation and [200] C. Ngaowthong, M. Bor uvka, L. Beha 
lek, P. Lenfeld, M. Svec, R. Dangtungee,
flame retardant behavior of the sisal fiber reinforced unsaturated polyester S. Siengchin, S.M. Rangappa, J. Parameswaranpillai, Recycling of sisal fiber
toughened epoxy nanocomposites, J. Appl. Polym. Sci. 132 (24) (2015). reinforced polypropylene and polylactic acid composites: thermo-
[177] Y.S. Park, C.W. Joo, Effects of nanoparticles on tensile, electrical, and thermal mechanical properties, morphology, and water absorption behavior, Waste
properties of Hemp/PBTG composites, Fibers Polym. 17 (11) (2016) Manag. 97 (2019) 71e81.
1934e1944. [201] G. Zhuo, X. Zhang, Y. Liu, M. Wang, Effect of multiple recycling on properties
[178] W. Pornwannachai, J.R. Ebdon, B.K. Kandola, Fire-resistant natural fibre- of poplar fiber reinforced high density polyethylene wood-plastic compos-
reinforced composites from flame retarded textiles, Polym. Degrad. Stabil. ites, Mater. Res. Express 6 (12) (2019) 125514.
154 (2018) 115e123. [202] B. Gewert, M.M. Plassmann, M. MacLeod, Pathways for degradation of plastic
[179] W. Pornwannachai, J.R. Ebdon, B.K. Kandola, Fire-resistant flax-reinforced polymers floating in the marine environment, Environmental science: Pro-
polypropylene/polylactic acid composites with optimized fire and mechan- cess. Impacts 17 (9) (2015) 1513e1521.
ical performances, J. Thermoplast. Compos. Mater. 33 (7) (2020) 898e914. [203] D. Åkesson, T. Fuchs, M. Sto €ss, A. Root, E. Stenvall, M. Skrifvars, Recycling of
[180] A. Subasinghe, A.A. Somashekar, D. Bhattacharyya, Effects of wool fibre and wood fiber-reinforced HDPE by multiple reprocessing, J. Appl. Polym. Sci.
other additives on the flammability and mechanical performance of poly- 133 (35) (2016).
propylene/kenaf composites, Compos. B Eng. 136 (2018) 168e176. [204] D.S. Bajwa, S. Bhattacharjee, Impact of Recycling on the Mechanical and
[181] B. Szolnoki, K. Bocz, P.L. So ti, B. Bodzay, E. Zimonyi, A. Toldy, B. Morlin, Thermo-Mechanical Properties of Wood Fiber Based HDPE and PLA Com-
K. Bujnowicz, M. Wladyka-Przybylak, G. Marosi, Development of natural posites, Handbook of Composites from Renewable Materials, 2017,
fibre reinforced flame retarded epoxy resin composites, Polym. Degrad. pp. 271e291.
Stabil. 119 (2015) 68e76. [205] D. Hammiche, A. Bourmaud, A. Boukerrou, H. Djidjelli, Y. Grohens, Number of
[182] B. Tawiah, B. Yu, S. Ullah, R. Wei, R. Yuen, J. Xin, B. Fei, Flame retardant poly processing cycle effect on the properties of the composites based on alfa
(lactic acid) biocomposites reinforced by recycled wool fibers-Thermal and fiber, J. Thermoplast. Compos. Mater. 29 (9) (2016) 1176e1193.
mechanical properties, Express Polym. Lett. 13 (8) (2019). [206] M. Tajvidi, A. Takemura, Recycled natural fiber polypropylene composites:
[183] J. Wang, H. Shi, P. Zhu, Y. Wei, P. Wei, J. Hao, Effect of natural basalt fiber for water absorption/desorption kinetics and dimensional stability, J. Polym.
EVA composites with nickel alginate-brucite based flame retardant on Environ. 18 (4) (2010) 500e509.
improving fire safety and mechanical properties, Polym. Adv. Technol. 31 (4) [207] M. Nazi Mwambegu, R. Gnanamoorthy, Water absorption in alkaline-treated
(2020) 713e721. coir pith e for use as reinforcement material in polymer matrix composites,
[184] W. Yang, Z. Jia, Y. Chen, Y. Zhang, J. Si, H. Lu, B. Yang, Carbon nanotube Mater. Today: Proc. 1 (2023) 9e14.
reinforced polylactide/basalt fiber composites containing aluminium hypo- [208] L. Rosenstock Vo €ltz, I. Di Guiseppe, S. Geng, K. Oksman, The effect of recy-
phosphite: thermal degradation, flame retardancy and mechanical proper- cling on wood-fiber thermoplastic composites, Polymers 12 (8) (2020) 1750.
ties, RSC Adv. 5 (128) (2015) 105869e105879. [209] M. Ahmadi, O. Zabihi, H.A. Nazarloo, K. Shirvanimoghaddam, X. Duan,
[185] X. Yu, Y. Pan, D. Wang, B. Yuan, L. Song, Y. Hu, Fabrication and properties of P. Adetunji, B. Egan, M. Naebe, Effects of melt-state shear homogenization on
biobased layer-by-layer coated ramie fabric-reinforced unsaturated poly- catalytic pyrolysis of mixed plastic waste for feedstock recycling, Materials
ester resin composites, Ind. Eng. Chem. Res. 56 (16) (2017) 4758e4767. Today Sustainability 22 (2023) 100343.
[186] X. Gao, D. Zhu, S. Fan, M.Z. Rahman, S. Guo, F. Chen, Structural and me- [210] D.B. Rocha, D.d.S. Rosa, Coupling effect of starch coated fibers for recycled
chanical properties of bamboo fiber bundle and fiber/bundle reinforced polymer/wood composites, Compos. B Eng. 172 (2019) 1e8.
composites: a review, J. Mater. Res. Technol. 19 (2022) 1162e1190. [211] H. Younesi-Kordkheili, A. Pizzi, Ionic liquid- modified lignin as a bio-
[187] R.A. Kurien, M. Maria Anil, S.L. Sharan Mohan, J. Anna Thomas, Natural fiber coupling agent for natural fiber- recycled polypropylene composites, Com-
composites as sustainable resources for emerging applications- a review, pos. B Eng. 181 (2020) 107587.
Mater. Today: Proc. 1 (2023) 1e9. [212] M. Laghaei, M. Ghasemian, W. Lei, L. Kong, Q. Chao, A review of boron
[188] M. Laghaei, C. Liu, Q. Li, M. Naebe, L. Kong, Mechanism of porosity devel- nitride-based photocatalysts for carbon dioxide reduction, J. Mater. Chem. A
opment and defect engineering in chemically activated woven carbon fibres, 11 (23) (2023) 11925e11963.
New J. Chem. 47 (31) (2023) 14610e14623. [213] N.S. Suharty, H. Ismail, K. Diharjo, D.S. Handayani, M. Firdaus, Effect of kenaf
[189] X. Zhao, K. Copenhaver, L. Wang, M. Korey, D.J. Gardner, K. Li, M.E. Lamm, fiber as a reinforcement on the tensile, flexural strength and impact
V. Kishore, S. Bhagia, M. Tajvidi, H. Tekinalp, O. Oyedeji, S. Wasti, E. Webb, toughness properties of recycled polypropylene/halloysite composites, Pro-
A.J. Ragauskas, H. Zhu, W.H. Peter, S. Ozcan, Recycling of natural fiber cedia Chem. 19 (2016) 253e258.
composites: challenges and opportunities, Resour. Conserv. Recycl. 177 [214] S. Xu, Y. Fang, Z. Chen, S. Yi, X. Zhai, X. Yi, J. He, Y. Song, Q. Wang, Impact of
(2022) 105962. lithium chloride on the performance of wood fiber reinforced polyamide 6/

27
M. Ahmadi, O. Zabihi, Z.K. Nia et al. Advanced Industrial and Engineering Polymer Research xxx (xxxx) xxx

high-density polyethylene blend composites, Polym. Compos. 40 (12) (2019) [227] H.M. Naguib, Recycled polyester filled with eggshells waste-based nano
4608e4618. CaCO3: thermo-mechanical and flame-retardant features, New J. Chem. 47
[215] O. Guselnikova, O. Semyonov, E. Sviridova, R. Gulyaev, A. Gorbunova, (10) (2023) 4999e5010.
D. Kogolev, A. Trelin, Y. Yamauchi, R. Boukherroub, P. Postnikov, “Functional [228] W. Zhang, P. Zhang, H. Wang, J. Li, S.Y. Dai, Design of biomass-based
upcycling” of polymer waste towards the design of new materials, Chem. renewable materials for environmental remediation, Trends Biotechnol. 40
Soc. Rev. 52 (14) (2023) 4755e4832. (2022) 1519e1534.
[216] J. Taibi, S. Rouif, B. Ame duri, R. Sonnier, B. Otazaghine, One-step multi- [229] H. Vahabi, M. Jouyandeh, T. Parpaite, M.R. Saeb, S. Ramakrishna, Coffee
functionalization of flax fabrics for simultaneous flame-retardant and hydro- wastes as sustainable flame retardants for polymer materials, Coatings 11 (9)
oleophobic properties using radiation-induced graft polymerization, Poly- (2021) 1021.
mers 15 (9) (2023) 2169. [230] S. Kulkarni, Z. Xia, S. Yu, W. Kiratitanavit, A.B. Morgan, J. Kumar, R. Mosurkal,
[217] Q. Huang, R. Hou, L. Lin, H. Li, S. Liu, Y. Cheng, X. Xu, Bioaccumulation and R. Nagarajan, Bio-based flame-retardant coatings based on the synergistic
trophic transfer of organophosphate flame retardants and their metabolites combination of tannic acid and phytic acid for nylonecotton blends, ACS
in the estuarine food web of the pearl river, China, Environ. Sci. Technol. 57 Appl. Mater. Interfaces 13 (51) (2021) 61620e61628.
(9) (2023) 3549e3561. [231] X. Almeras, M. Le Bras, P. Hornsby, S. Bourbigot, G. Marosi, P. Anna,
[218] R.A. Ilyas, H.A. Aisyah, A.H. Nordin, N. Ngadi, M.Y.M. Zuhri, M.R.M. Asyraf, R. Delobel, Effect of recycling on fire retardancy of intumescent poly-
S.M. Sapuan, E.S. Zainudin, S. Sharma, H. Abral, M. Asrofi, E. Syafri, N.H. Sari, propylene based blends, progress in rubber, Plastics and Recycling Tech-
M. Rafidah, S.Z.S. Zakaria, M.R. Razman, N.A. Majid, Z. Ramli, A. Azmi, S.P. Bangar, nology 20 (1) (2004) 25e45.
R. Ibrahim, Natural-fiber-reinforced chitosan, chitosan blends and their nano- [232] S.V. Levchik, G.R. Alessio, Y. Yang, Flame Retardant Polyolefin Composition
composites for various advanced applications, Polymers 14 (5) (2022) 874. for Shipping Pallets, Google Patents, 2014.
[219] L. Dong, Y. Xue, H. Huang, D. Shen, W. Gao, F. Xu, Y. Weng, Y. Zhang, Facile [233] F. Hewitt, T.R. Hull, Mineral filler fire retardants, in: S. Palsule (Ed.), Polymers
synthesis of soybean protein-based phosphorus-nitrogen flame retardant for and Polymeric Composites: A Reference Series, Springer Berlin Heidelberg,
poly(lactic acid), Polym. Degrad. Stabil. 214 (2023) 110412. Berlin, Heidelberg, 2016, pp. 1e26.
[220] S. Weng, Z. Li, C. Bo, F. Song, Y. Xu, L. Hu, Y. Zhou, P. Jia, Design lignin doped [234] H. Horacek, R. Grabner, Advantages of flame retardants based on nitrogen
with nitrogen and phosphorus for flame retardant phenolic foam materials, compounds, Polym. Degrad. Stabil. 54 (2) (1996) 205e215.
React. Funct. Polym. 185 (2023) 105535. [235] M. Kaplan, M. Ciesielski, S. Fuchs, C. Getterle, F. Scho € nberger,
[221] M. Marcioni, M. Zhao, L. Maddalena, T. Pettersson, R. Avolio, R. Castaldo, R. Pfaendner, Novel macromolecular and biobased flame retardants based
L. Wågberg, F. Carosio, Layer-by-Layer-Coated cellulose fibers enable the on cellulose esters and phosphorylated sugar alcohols, Polymers 15 (15)
production of porous, flame-retardant, and lightweight materials, ACS Appl. (2023) 3195.
Mater. Interfaces 15 (30) (2023) 36811e36821. [236] C. Ling, L. Guo, Z. Wang, A review on the state of flame-retardant cotton
[222] P. Liu, J. Ling, T. Mao, F. Liu, W. Zhou, G. Zhang, F. Xie, Adhesive and flame- fabric: mechanisms and applications, Ind. Crop. Prod. 194 (2023) 116264.
retardant properties of starch/Ca2þ gels with different amylose contents, [237] M. Ahmadi, O. Zabihi, R. Yadav, M.R.G. Ferdowsi, M. Naebe, The reinforcing
Molecules 28 (11) (2023) 4543. role of 2D graphene analogue MoS2 nanosheets in multiscale carbon fibre
[223] H. Xinsheng, G. Yang, Q. Zhang, Application status and development pros- composites: improvement of interfacial adhesion, Compos. Sci. Technol. 207
pects of bio-based flame retardants in packaging materials, European Journal (2021) 108717.
of Wood and Wood Products 81 (2023) 1337e1357. [238] M. Ahmadi, O. Zabihi, R. Yadav, M.R. Ghandehari Ferdowsi, M. Naebe, Co-
[224] P. Widsten, S. Salo, T. Hakkarainen, T.L. Nguyen, M. Borrega, O. Fearon, Antimi- valent treatment of carbon fibre with functionalized MoS2 nanosheets using
crobial and flame-retardant coatings prepared from nano- and microparticles of thiol-ene click chemistry: the improvement of interface in multiscale epoxy
unmodified and nitrogen-modified polyphenols, Polymers 15 (4) (2023) 992. composites, Compos. B Eng. 236 (2022) 109821.
[225] H. Yue, J. Wang, H. Wang, Z. Du, X. Cheng, X. Du, Flame-retardant and form- [239] M. Ahmadi, O. Zabihi, S. Jeon, M. Yoonessi, A. Dasari, S. Ramakrishna,
stable phase-change composites based on phytic acid/ZnO-decorated sur- M. Naebe, 2D transition metal dichalcogenide nanomaterials: advances,
face-carbonized delignified wood with superior solar-thermal conversion opportunities, and challenges in multi-functional polymer nanocomposites,
efficiency and improved thermal conductivity, ACS Appl. Mater. Interfaces 15 J. Mater. Chem. A 8 (3) (2020) 845e883.
(6) (2023) 8093e8104. [240] M. Ahmadi, O. Zabihi, Q. Li, S.M. Fakhrhoseini, M. Naebe, A hydrothermal-
[226] J. Ren, Y. Wang, J. Piao, J. Cui, H. Guan, C. Jiao, X. Chen, Facile construction of assisted ball milling approach for scalable production of high-quality func-
phosphorus-free and green organic-inorganic hybrid flame-retardant sys- tionalized MoS2 nanosheets for polymer nanocomposites, Nanomaterials 9
tem: for improving fire safety of EP, Prog. Org. Coating 179 (2023) 107489. (10) (2019) 1400.

28