International Journal of Biological Macromolecules 305 (2025) 141130

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

A review of fire performance of plant-based natural fibre reinforced

polymer composites
Mohammed Huzaifa Mulla a,b, Mohd Nurazzi Norizan a,b,* , Nurul Fazita Mohammad Rawi a,b ,
Mohamad Haafiz Mohamad Kassim a,b , Che Ku Abdullah a,b, Norli Abdullah c ,
Mohd Nor Faiz Norrrahim d
a
Bioresource Technology Division, School of Industrial Technology, Universiti Sains Malaysia, Penang 11800, Malaysia
b
Green Biopolymer, Coatings & Packaging Cluster, School of Industrial Technology, Universiti Sains Malaysia, Penang 11800, Malaysia
c
Centre for Defence Foundation Studies, Universiti Pertahanan Nasional Malaysia, Kem Perdana Sungai Besi, Kuala Lumpur 57000, Malaysia
d
Research Center for Chemical Defence, Universiti Pertahanan Nasional Malaysia, Kem Perdana Sungai Besi, Kuala Lumpur 57000, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Natural fibre from plant-based reinforced polymer composites (NFRPCs) offers an attractive solution for various
Natural fibre applications due to their cost-effectiveness, sustainability, and favourable properties. These materials provide
Polymer composites high strength and stiffness while remaining lightweight, which is especially advantageous in weight-sensitive
Thermal
applications. However, their susceptibility to high flammability poses a significant challenge for applications
Flammability
Fire resistance
requiring robust fire resistance. Consequently, researchers and engineers face the primary task of enhancing
flame retardancy and thermal stability in NFRPCs. This paper provides a comprehensive review of the flam­
mability and flame retardancy aspects of NFRPCs, delving into critical elements such as modification methods,
the interfacial bond between natural fibres and the polymer matrix, fibre type, loading ratio, fibre orientation,
polymer type, and composite structure. Understanding these factors is crucial for improving material fire
resistance. The paper explores various flame-retardant strategies for NFRPCs, including additives, coatings,
treatments, and nanomaterial hybridization. Detailed insights into mechanisms and characterization techniques
related to thermal and flame retardancy are provided, covering aspects like thermal degradation, char formation,
gas-phase reactions, fire testing methods, universally accepted standards, and specific flame-retardant re­
quirements for NFRPCs in diverse applications such as automotive, aerospace, marine, and civil construction.
The discussion on future directions emphasizes the development of innovative flame-retardant materials,
improving composite design and fabrication improvements, and assessing fire performance and environmental
impact.

1. Introduction significant drawback lies in contributing to environmental pollution due

to their non-biodegradable composition. Consequently, natural fibres
Natural fibre from plants has emerged as a highly promising alter­ serve as a compelling and eco-friendly substitute for synthetic fibres.
native in lightweight manufacturing and engineering sectors, offering These lignocellulosic fibres are incorporated into the polymer matrix to
economic and environmental benefits. These fibres are characterized by fabricate polymer composites [1,2]. Fig. 1 depicts various natural fibre
their biodegradability, recyclability, and lignocellulosic nature, pre­ sources derived from plants, including kenaf stem [3], coconut sheaths
senting numerous advantages over their synthetic counterparts. [4], oil palm fibre [5], sugar palm fibres [6], sisal [7], flax [8], jute [9],
Notably, natural fibres exhibit non-abrasive properties, require minimal coir [10], and bamboo [11]. These fibres, renowned for their excep­
energy consumption, possess a high aspect ratio, and have low density, tional strength, durability, and versatility, are extensively employed in
making them cost-effective. Additionally, their biodegradable nature various engineering applications [12,13]. These properties highlight
aligns with sustainability goals. In contrast, synthetic-reinforced poly­ natural fibres' diversity and specific applications based on their me­
mer composites may excel in certain mechanical properties, but their chanical strength, flexibility, density, stiffness, chemical composition,

* Corresponding author at: Bioresource Technology Division, School of Industrial Technology, Universiti Sains Malaysia, Penang 11800, Malaysia.
E-mail address: [email protected] (M.N. Norizan).

https://doi.org/10.1016/j.ijbiomac.2025.141130
Received 2 April 2024; Received in revised form 26 January 2025; Accepted 14 February 2025
Available online 16 February 2025
0141-8130/© 2025 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

and thermal conductivity. The comparison of mechanical and chemical treatments or blending with less flammable materials essential for ap­
properties and thermal conductivity of plant-based natural fibres' are plications that require enhanced fire resistance.
shown in Table 1. Incorporating fillers such as fibres or particles into polymers enables
Table 1 provides a comprehensive comparison of various natural the fabrication of composite materials with tailored mechanical, ther­
fibres, focusing on their mechanical, physical, and chemical properties, mal, and electrical properties. Natural fibres, in particular, are gaining
which are key to determining their suitability for different applications. prominence as reinforcements within these polymer matrices, offering a
Sugar palm fibre has a moderate tensile strength (170–230 MPa), low viable alternative to traditional materials. The characteristics of these
elongation at break (1.2–1.6 %), and a density of 1.4 g/cm3, making it composites primarily depend on fibre attributes and microstructural
suitable for lightweight applications. Coir fibre stands out with high factors, including fibre diameter, length, distribution, orientation, vol­
elongation (15–30 %) and significant decay resistance due to its high ume fraction, and packing arrangement. While NFRPCs are increasingly
lignin content (41–45 %). Flax and hemp fibres are notable for their high used in structural applications, their market potential has been some­
tensile strength (up to 1500 MPa and 900 MPa, respectively) and stiff­ what limited by their restricted toughness. However, mechanical prop­
ness (Young's modulus of 27.6 GPa and 70 GPa). Cotton fibre, with the erties can be significantly improved by hybridizing natural fibres with
highest cellulose content (90 %), provides strength but lacks rigidity due synthetic ones [43–46].
to its low lignin content (0.75 %). Thermal conductivity is low across These attributes render composites highly attractive for diverse ap­
most fibres, making them suitable for insulation, with bamboo fibre plications, ranging from aerospace to construction. The future holds
having the highest thermal conductivity (0.2061 W/m K) and sugar promise for these versatile materials as their applications continue to
palm fibre at 0.04 W/m K. expand and evolve [47]. NFRPCs have ushered in a paradigm shift in
Flammability is a critical factor when selecting natural fibres, structural design and engineering, underscoring their effectiveness
particularly for use in textiles and building materials where fire resis­ across various applications, including automobiles, aircraft, civil infra­
tance is essential. Many natural fibres, such as cotton, jute, flax, hemp, structure, and wind energy. The remarkable surge in the popularity of
and coir, exhibit moderate to high flammability due to their high cel­ NFRPCs highlights their potential [44,45,48–51]. It is truly fascinating
lulose content, which is inherently combustible. Cotton, with its 89 % to observe advancements in this field, particularly in utilizing natural
cellulose content, is particularly flammable, burning rapidly once and bio-based fibres and exploring recycling possibilities at the end of
ignited. Flax and hemp fibres, which have cellulose contents of 71–71.5 their lifecycle.
% and 57–77 %, respectively, are also flammable but may burn more While natural fibre composites offer many benefits, they face chal­
slowly than cotton due to their higher density and lower elongation at lenges, particularly their inherent flammability, which limits their fire
break. Despite coir's high lignin content (41–45 %), which usually pro­ resistance compared to non-flammable materials like glass or carbon
motes charring and can slow combustion, it remains flammable. fibre composites. The inherent characteristics of these composites, such
Fibres such as sugar palm and kenaf, with substantial hemicellulose as the hydrocarbon-based polymers and the cellulose found in plant fi­
content (32.2 % and 21.5 %, respectively), tend to burn more slowly bres, contribute to their flammability. The thermal decomposition of
than those with higher cellulose content, as hemicellulose tends to char these materials typically occurs between 300 and 500 ◦ C, producing
rather than ignite easily. Bamboo fibre, due to its varying density and both gaseous and condensed phases. This process generates various by-
relatively low thermal conductivity, may exhibit different flammability products, including combustible gases, liquids, char, smoke, and drips,
characteristics, potentially offering better fire resistance due to its all of which pose potential hazards to human health [52,53]. Balancing
structure and lower density. Overall, the high organic content of these the mechanical and fire performance of composites is challenging. His­
natural fibres highlights their flammability, making flame-retardant torically, the focus has been on optimizing physical and mechanical

Fig. 1. Examples of plant-based natural fibres that are potentially used as reinforcements.

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Table 1
Comparison of the mechanical properties of natural fibres.
Natural Tensile Elongation at Density Young's Modulus Chemical composition in % Thermal Ref.
Fibre Strength Break (%) (g/cm3) (GPa) Conductivity (W/
Cellulose Hemicellulose Lignin
(MPa) m K)

Sugar Palm 170–230 1.2–1.6 1.4 3.5–4.5 43.7 32.2 26 0.04 [14–16]
Fibre
Coir Fibre 175–220 15–30 1.2 4–6 36–43 0.15–0.25 41–45 0.04 [17–20]
Jute Fibre 393–773 1.5–1.8 1.3 26.5 33.4 22.7 28 0.14 [20–22]
Flax Fibre 345–1500 1.5–3.2 1.5 27.6 71 18.6–20.6 2.2 0.05 [20,23–26]
Hemp Fibre 550–900 1.6 1.48 70 68 15 10 0.05 [20,27–30]
Kenaf Fibre 280 1.6 1.2 53 72 20.3 9 0.051–0.058 [20,31–33]
Bamboo 140–230 2.5–3.7 0.6–1.1 11–17 26–43 30 21–31 0.2061 [20,32–34]
Fibre
Cotton Fibre 287–800 3–10 1.5–1.6 5.5–12.6 90 4 0.75 0.07 [20,35,36]
Pineapple 400–627 14.5 0.8–16 1.44 70–82 18.0 5–12 0.026–1.0 [20,37,38]
Fibre
Banana 355 53 1.35 33.8 60–65 6–8 5–10 0.045 [20,39,40]
Fibre
Ramie Fibre 560 2.5 1.5 24.5 68.6–76.2 13–16 0.6–0.7 0.126–0.152 [20,41,42]

properties, while fire resistance received less attention. However, the structure contributes to natural fibres having both high stiffness and
development of flame retardant technologies has become increasingly flexibility while at the same time facilitating lighter weight in the
significant in addressing these challenges [54]. composites. Their densities range between 0.6 and 1.6 g/cm₃, which
Integrating flame-resistant composites into various applications is provides a value in weight attenuation, particularly in the automotive,
critical in today's landscape. This necessity stems from the swift ad­ aerospace, and construction industries, where weight plays a crucial role
vancements in flame retardant technology geared toward augmenting [66]. The other necessary advantages are the biocompatibility and the
safety and broadening the potential applications of these polymer renewability of the fibres. Unlike synthetic fibres made from non-
composites across industries. The chief goal is to enhance the safety and renewable petrochemical feedstock, agricultural fibres can be grown
longevity of these materials while diversifying their usage across again and again with less environmental impact. There is also a growing
different sectors [55]. The flammability of composites is defined by the trend in the global development of carbon emission reduction and waste
initiation and propagation of a fire, with crucial parameters including minimisation, which is one reason for exploring new exclusive uses of
limiting oxygen index (LOI) [56], time-to-ignition (TTI) [57], total heat plant materials [67,68]. In addition, plant fibres' tensile strength is
release (THR) [58], peak heat release rate (pHRR) [59], and- flame higher than that of synthetic fibres, with plant fibres rated at 170–1500
spread rate [60]. Factors such as total smoke production (TSP) [60], MPa—varying in strength as dispensed within numerous fibre types
smoke density [61], and smoke toxicity [62] hold paramount impor­ [69,70].
tance as they directly influence human survival during a fire incident. Plant-based fibres possess unique microstructural characteristics that
Despite their potential, the notable flammability of polymers remains a set them apart from synthetic fibres. The hierarchical arrangement of
significant challenge, necessitating extensive research into thermal cellulose microfibrils and amorphous regions in plant fibres provides a
decomposition and fire resistance; among various strategies, incorpo­ structured architecture that facilitates interfacial bonding with polymer
rating flame retardants has proven particularly effective in mitigating matrices. However, the hydrophilic nature of plant fibres, due to the
fire hazards [63]. presence of hydroxyl groups, contrasts with the typically hydrophobic
A promising avenue for enhancement is hybridization, where com­ nature of most polymer matrices, posing challenges for effective
posites incorporate one or more reinforcement fibres to bolster me­ adhesion.
chanical, thermal strength, and fire resistance characteristics. These Surface modification techniques, such as alkaline treatments and the
composite structures, often utilizing fibres with a specific focus on nat­ use of coupling agents, can address this issue by reducing the hydro­
ural fibres, aim to amplify mechanical performance. The synergy ach­ philicity of plant fibres and improving their compatibility with polymer
ieved by combining multiple reinforcement fibres significantly enhances matrices. These treatments enhance bonding by increasing surface
material strength and impact resistance while maintaining cost- roughness and exposing reactive sites, which promote better mechanical
effectiveness [64,65]. Advancing flame-retardant solutions to bolster interlocking and chemical bonding at the interface. When these factors
the flame resistance of NFRPCs remains a primary focus of ongoing are optimized, efficient load transfer occurs, significantly improving the
research. Despite significant advancements, a more comprehensive composite's mechanical performance and durability [71–73]. This
research framework is needed to fully decipher and enhance the flame characteristic is essential, especially for coping with the demands of
resistance properties of these materials. Understanding the fire impacts structural applications, which require materials that can easily be
on natural fibres and their composites holds crucial importance. This configured in anticipation of dynamic loads. Plant fibres also have very
study integrates and interprets earlier research outcomes on the influ­ high sound absorption capacity, which is not found in many synthetic
ence of fire and flammability on fibre and related attributes, widening materials. This makes them dependable for sound-absorbing vehicles
the understanding of NFRPCs. The review aims to provide valuable in­ and architectural applications such as noise control. The excellent vi­
sights for their enhanced practical usage, addressing key challenges such bration absorption by the plant's fibres makes them better materials for
as thermal stability and flammability. This initiative underscores our use in applications that require damping than synthetic materials
commitment to promoting the understanding and application of NFRPCs [73–75].
in the polymer industry.
2. Thermal and flammability characteristics of natural fibre
reinforced polymer composites
1.1. Plant fibre features: microstructure and functional characteristics
In the mechanical, civil, automotive engineering, and aviation sec­
Plant fibres possess some unique features of a lignocellulosic struc­ tors, fibre-reinforced polymer composites are growing, particularly
ture generally composed of cellulose, hemicellulose, and lignin. This

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those derived from natural fibres. While these materials offer significant Natural fibres, primarily composed of cellulose, hemicellulose,
mechanical and sustainability advantages, ensuring their adequate lignin, wax, pectin, and minor components like extractives, showcase a
protection against fire is crucial to meeting safety standards in these complex structure [89]. Cellulose, the structural foundation, forms a
industries [62,76]. Understanding and addressing fire risks are pivotal crystalline structure from interconnected glucose units in elongated
for their widespread adoption, safeguarding lives and properties. The chains. Hemicellulose, acting as an adhesive matrix between micro-
behaviour of the polymer when subjected to high temperatures, cellulose fibrils, contributes as the primary structural element of the
including factors like melting point, degradation temperature, and heat fibre cell [92]. Cellulose's thermal decomposition occurs in multiple
of combustion, significantly impacts the composite's fire performance stages, beginning with absorbed water desorption, then cellulose chain
[77]. Hence, carefully selecting a polymer matrix with appropriate fire cross-linking, releasing water to form dehydrocellulose. Subsequent
and thermal properties tailored to the specific application is paramount. dehydrocellulose decomposition generates char and volatiles, ultimately
Natural plant-based fibres exhibit distinct structural features, such as resulting in levoglucosan formation. The final stage involves levoglu­
hollow cores, which present both opportunities and challenges for cosan decomposition, producing flammable and non-flammable vola­
managing heat flux. These hollow cores trap air, a poor heat conductor, tiles, tar, gases, and char [93,94]. These intricate materials, products of
enhancing the thermal insulation capabilities of the composites. For nature, boast a diverse range of properties. Delving into natural fibres
instance, plant fibre composites like jute demonstrate thermal conduc­ and their characteristics represents a crucial research area, offering
tivities ranging between 0.036 and 0.044 W/m K, comparable to syn­ numerous potential applications across various industries [89,95].
thetic counterparts such as glass fibres [78–80]. This property makes Cellulose and lignin are the primary components in natural fibres,
plant-based composites highly effective as insulators, especially under dictating their flammability [96]. Cellulose undergoes thermal degra­
low heat flux conditions. The thermal resistance of natural fibre com­ dation, occurring roughly between 260 ◦ C and 350 ◦ C, producing
posites is influenced by factors such as fibre diameter, thickness, and flammable volatiles and gases alongside non-combustible gases, tars,
area density. Optimizing these parameters involves tailoring fibre di­ and a certain amount of char [93,94,97]. In contrast, hemicellulose
mensions to balance thermal insulation with mechanical strength, decomposes between temperatures of 200 ◦ C and 260 ◦ C, yielding a
selecting fibres with suitable area density for specific applications, and greater quantity of non-combustible gases and a lesser amount of tar
adjusting thickness to minimize heat transfer. These optimizations are than cellulose [97]. Lignin begins its decomposition process around
driven by application-specific requirements, such as achieving target 160 ◦ C, continuing up to approximately 400 ◦ C. Throughout this phase,
thermal conductivity levels or enhancing energy efficiency in insulation weaker bonds within lignin break at lower temperatures, while the
materials [80,81]. For example, incorporating hollow microspheres or severance of stronger bonds, found in the aromatic rings, occurs at
lightweight fillers, such as hollow glass microspheres, creates multiple higher temperatures. This intricate process highlights the elaborate
thermal resistance pathways, reducing overall heat transfer [82,83]. nature of natural fibres and their response to fire [98].
Similarly, chemical treatments like alkaline processing enhance fibre Chemical treatments offer an alternative method to enhance the fire
compatibility with polymer matrices, leading to improved mechanical resistance of natural fibre-reinforced polymer composites. These treat­
and thermal properties [83,84]. ments modify the surface properties of the fibres, reducing their sus­
Despite their thermal advantages, natural fibres pose significant ceptibility to ignition and combustion. Moreover, they can improve the
flammability risks due to their inherent combustibility. Unlike synthetic adhesion between fibres and the polymer matrix, enhancing the overall
fibres, natural fibres provide additional fuel during combustion, result­ composite performance [99,100]. Several techniques are employed to
ing in earlier ignition and higher heat release rates (HRR) [85]. Studies bolster the fire resistance of these composites. One such method involves
comparing flax fibre-reinforced composites to glass fibre composites of using fire retardants (FRs) incorporated during manufacturing or
similar architecture show that the former exhibit greater total heat applied as a coating post-production. These substances diminish the heat
release (THR) and prolonged flameout times [86]. The hollow core release rate and slow flame spread, affording more time for evacuation
structure of natural fibres exacerbates these challenges by facilitating and response during a fire incident [101,102]. Altering the surface
heat transfer and the release of pyrolysis gases, thereby accelerating properties of fibres significantly reduces the propensity of composite
flame spread and structural deformation during combustion. Tests such materials to ignite, proving more effective than integrating flame re­
as cone calorimetry and vertical burn assessments confirm rapid igni­ tardants into the composites. The fire behaviour of natural fibres de­
tion, increased mass loss rates, and significant structural shrinkage pends on factors like fibre constituents, weight percentage, and
[86,87]. structural morphology [103]. Additionally, numerous other elements
Several strategies have been developed to address these flammability contribute to flammability.
challenges. The incorporation of fire retardants (FRs) during
manufacturing or as post-production coatings is one effective approach. 3. Factors affecting the flammability of NFRPCs
Ammonium polyphosphate (APP), for instance, enhances fire resistance
by forming protective char layers that slow down flame spread. Chem­ The flammability and thermal behaviour of NFRPCs are influenced
ical treatments like alkali and silane modifications not only improve by several key factors, including fibre volume content, matrix type,
fibre-matrix adhesion but also enhance thermal stability, further surface treatment of fibres, and filler concentration. These factors
contributing to fire performance [84,88]. Hybrid composites, which collectively determine the composite's fire performance and thermal
combine natural and synthetic fibres, offer a balanced approach by stability. Researchers utilize various techniques to evaluate these
leveraging the thermal and fire-resistant properties of both materials. properties, such as LOI tests to measure the minimum oxygen concen­
In-depth analysis of thermal and flammability characteristics is tration required for combustion, flame tests, cone calorimetry, and the
essential for understanding and improving natural fibre composites. UL 94 test to assess heat release rates. Understanding these influences is
Thermal analysis techniques, which track temperature changes, heat critical for optimizing NFRPC performance, enabling their application in
flow, and other thermal properties, provide critical insights into mate­ diverse fields while addressing challenges like flammability and thermal
rial behaviour under varying conditions [89,90]. Flammability analysis, stability [104,105].
on the other hand, evaluates a material's ignition potential, combustion
propensity, and susceptibility to incineration. These assessments are 3.1. Chemical composition
particularly important for materials exposed to oxygen-rich environ­
ments, where the likelihood of combustion increases. By analysing these The flammability of natural fibres is intricately linked to their
properties, researchers can guide the development of safer and more chemical composition, which includes key components such as cellu­
effective composite materials [91]. lose, hemicellulose, lignin, pectin, and plant waxes. Each of these

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constituents plays a distinct role in how natural fibres respond to fire retardant properties of natural fibres, although the improvement was
conditions, influencing their combustion characteristics. Cellulose, the limited due to the insufficient release of inert nitrogen gas. Pillai et al.
primary structural polymer found in natural fibres, is characterized by [119] reported that the incorporation of molybdenum disulfide into coir
long chains of glucose units. While its crystalline structure imparts fibre composites can decrease the temperature and promote the for­
strength and thermal stability, it does not significantly mitigate flam­ mation of inert products during combustion, thereby enhancing fire
mability. Cellulose is highly combustible and ignites readily, releasing resistance. The modification of the fibre-matrix interface has also been
volatile gases during combustion that can sustain a fire [53,94]. Hemi­ explored as a means to improve the fire performance of plant-based fibre
celluloses are polysaccharides with lower molecular weights and greater composites. Soni et al. [120] found that the combination of alkali and
hydrophilicity compared to cellulose, which impacts the thermal and silane treatment on hemp fibres resulted in improved mechanical
flammability characteristics of plant fibres. They decompose at rela­ properties and reduced flammability, as indicated by increased limiting
tively low temperatures, releasing volatile gases that contribute to oxygen index (LOI) values. In addition to chemical modifications, the
ignition and rapid burning. The presence of hemicellulose within the physical orientation of fibres within the composite structure can also
fibre matrix significantly affects the thermal decomposition behaviour influence the combustion behaviour.
and increases the flammability of the material. Surface modification Xu et al. [116] investigated the thermal and fire behaviour of natural
techniques, such as alkaline treatments, can reduce hemicellulose con­ fibre-reinforced polymer composites and found that the pHRR was lower
tent, improving thermal stability and reducing the flammability of plant for the natural fibre composites compared to the pure polymer. How­
fibres when incorporated into polymer composites [94,106,107]. ever, the researchers noted that the hollow cores of the plant-based fi­
Lignin, a complex aromatic polymer, uniquely affects flammability bres could still contribute to the overall combustibility of the material.
due to its amorphous structure and higher molecular weight. Unlike The hollow structure may allow for the rapid penetration of heat and the
cellulose and hemicellulose, lignin tends to burn more slowly, often formation of combustible volatiles, which can further propagate the fire
forming a protective char layer that can help retard further combustion. [117]. Eibl et al. [121] observed that the out-of-plane fibre orientation
However, it still serves as a fuel source once the other components in carbon fibre-reinforced polymer composites affected the heat release
ignite, and its contribution to the overall flammability of natural fibres is rate (HRR) curves, with low-angle specimens exhibiting distinct HRR
significant [108,109]. Pectin, although present in smaller quantities, peaks typical of charring and delaminating composites. While the
also influences the flammability of natural fibres by affecting their combustibility of plant-based fibres poses challenges, the research ef­
structural integrity. Upon exposure to heat, pectin degrades, which can forts summarised here demonstrate the potential for developing effec­
weaken the fibre and increase its susceptibility to ignition. While its tive solutions to enhance the fire safety of these materials. By leveraging
impact is less pronounced than that of cellulose or hemicellulose, it a combination of chemical modifications, the incorporation of flame
nonetheless contributes to the fire behaviour of the fibre [110,111]. retardants, and the optimization of fibre orientation, it is possible to
Plant waxes, composed of long-chain aliphatic hydrocarbons, further mitigate the combustibility issues and enable the broader adoption of
contribute to the flammability of natural fibres. When subjected to heat, plant-based fibres in various applications [122,123].
these waxes can melt and volatilize, releasing flammable components
that facilitate ignition. The specific impact of plant waxes varies 3.2. Chemical treatments
depending on their composition and the type of fibre, but their presence
generally enhances the combustibility of the fibres [112,113]. The The flammability of NFRPCs is significantly influenced by the
natural composition of fibres, influenced by cellulose, hemicellulose, matrices used, which can be altered through various chemical treat­
lignin, pectin, and plant waxes, contributes to their flammability. Each ments. These treatments can modify the surface properties of the fibres,
component interacts in complex ways during combustion, and under­ enhancing their adhesion to the polymer matrix and thereby increasing
standing these interactions is crucial for developing flame-retardant the composite's thermal stability [124,125]. Additionally, treatments
treatments or selecting fibres for applications where fire resistance is such as silane and fluorocarbon can reduce the moisture absorption of
essential. natural fibres, a common issue that can negatively impact the compos­
The combustibility of plant-based fibres is primarily attributed to ite's mechanical and flammability properties [126].
their chemical composition, which is dominated by cellulose, hemicel­ Applying coupling agents, like lysine-based diisocyanate (LDI), can
lulose, and lignin [114]. Cellulose, the main structural component, is further augment the composite's thermal stability. Moreover, specific
highly flammable and can contribute to the rapid spread of flames treatments have been observed to boost the thermal performance of
[115]. Hemicellulose, another major constituent, also exhibits high NFRPCs [124,125]. For instance, plasma surface treatment applied to
combustibility, while lignin, though less flammable, can still release PET fabric nanoparticle composites has enhanced thermal stability and
combustible volatiles during pyrolysis [114]. Several studies have altered combustion behaviour. Similarly, utilizing lysine-based diiso­
investigated the relationship between the chemical composition of cyanate (LDI) as a coupling agent in bamboo fibre-based biocomposites
plant-based fibres and their combustion characteristics. Dorez et al. has shown a certain degree of improvement in thermal stability
[114] found a correlation between the lignin content and various [127–129]. Additionally, observations indicate that silane treatment
combustion parameters, such as char yield, effective heat of combustion, enhances the storage modulus of kenaf/PLA composites and positively
and the ratio of carbon monoxide to carbon dioxide during cone calo­ impacts their thermal stability. Surface treatment with NaOH has also
rimeter tests. This suggests that the relative proportions of these key been noted to improve the thermal performance of Borassus fruit fibre/
components can significantly influence the overall flammability of the polypropylene (PP) composites when MAPP is used as a compatibilizer
fibres. To address the combustibility issues, researchers have explored [129,130].
various strategies for improving the fire retardancy of plant-based fibres
and their composites. One approach is the use of flame retardant 3.3. Type of matrices
treatments, such as the application of chemical modifications or coatings
[116,117]. For example, Xu et al. [116] developed a highly flame- The choice of polymer matrix significantly impacts the fire-retardant
retardant blend fibre by combining flame-retardant alginate fibre with characteristics of plant fibre-reinforced polymer laminates. The com­
polyester fibre, which met the requirements for use in combustion- posite's fire behaviour can vary depending on the specific polymer
sensitive applications. properties. For instance, In the context of natural fibre-reinforced
Another approach involves the incorporation of inert or flame- polymer composites, the fire resistance of thermoplastic polymers such
retardant additives into the fibre-reinforced composites. Peng et al. as PP and PE can be enhanced by incorporating flame retardants or other
[118] investigated the use of urea treatment to improve the fire fire-resistant agents into the polymer matrix. While these thermoplastics

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are known for their high flammability and rapid mass loss rates, the extensively studied across various fields due to their profound impact on
addition of flame retardants significantly improves their fire perfor­ material properties and safety considerations. The size of fibre particles
mance, making them more suitable for fire-retardant applications. On is a crucial determinant of their combustion characteristics. Research in
the other hand, thermosetting polymers like epoxy and polyester exhibit flammability and dust explosions, especially concerning fossil fuels, has
higher ignition temperatures and heat release rates compared to ther­ consistently demonstrated a clear correlation between particle size and
moplastics. These polymers are more thermally stable and resistant to ignition propensity: smaller particles are more prone to ignition and
deformation under heat. However, they do not inherently offer sufficient often lead to more severe combustion outcomes. This increased risk is
fire resistance unless modified with flame retardants. In summary, both attributed to smaller particles' larger surface area-to-mass ratio, which
thermoplastics and thermosetting polymers require the incorporation of enhances their reactivity and accelerates the heating process
flame retardant treatments to achieve adequate fire resistance, making [113,141–143].
the integration of flame retardants essential for improving fire safety in Due to the critical nature of this relationship, preventive measures
both types of polymers [131]. During curing, these undergo irreversible are commonly implemented in high-risk environments such as mines
chemical reactions, resulting in a rigid, heat-resistant 3D network of and coal storage facilities to reduce the presence of fine particles and
covalent bonds. Unlike thermoplastics, which can be reshaped by heat, mitigate explosion hazards. However, despite its importance, there is no
thermosets cannot be recycled through thermal means due to their universally standardized definition of particle size. Typically, “particle
permanent crosslinked structure. size” is expressed as the median diameter (d50), indicating that 50 % of
While thermoplastic matrix composites are less prevalent in engi­ the particle distribution falls below this size by volume or mass. Other
neering applications, advancements in impregnation techniques—such parameters such as d10, d90, and specific surface area (SSA) are often
as polymer melting, solvent-based methods, and low-viscosity pre­ reported to provide a more comprehensive understanding of the particle
cursors—can overcome impregnation challenges. Recyclability and size distribution. The dxx values represent the particle sizes below which
specific properties like increased toughness give fibre-reinforced ther­ xx% of the particles lie, while SSA measures the surface area relative to
moplastic matrix composites a competitive advantage. These thermo­ the mass of the particles [141,144]. Controlling particle size distribution
plastic matrices are used in non-structural and structural contexts in natural fibres is essential for applications where flammability is a
[72,132–134]. Eibl and Swanson [121] investigated the impact of car­ concern. Due to their increased surface area, fine fibre particles signif­
bon fibre orientation on the fire behaviour of epoxy-based composites icantly heighten the likelihood of ignition and intensify the severity of
using cone calorimetry. Their findings revealed that out-of-plane fibre fires or explosions. Therefore, understanding and managing the particle
orientation affects heat emission during a fire, with the pyrolysis size distribution of natural fibres is crucial for reducing fire hazards. This
frontline moving faster when parallel to the fibres compared to can be achieved by employing flame retardant treatments or optimizing
perpendicular orientations [135,136]. fibre processing techniques for safer particle sizes.
In the context of lightweight construction and manufacturing, the In addition to particle size, the shape of fibre particles is another
thermal properties of polymeric matrices are crucial. These matrices are critical factor influencing their combustion behaviour. Particle shape is
inherently susceptible to thermal degradation, adversely affecting their defined by the relative dimensions of a particle's long, intermediate, and
flammability behaviour. Interestingly, the thermal resistance of com­ short axes. For example, spherical particles have a higher volume-to-
posite materials primarily depends on the reinforcements and fillers surface area ratio (aspect ratio) than cylindrical particles of the same
rather than the polymer matrix itself. Notably, natural fibre re­ volume. This difference means particle with lower aspect ratios, such as
inforcements can compromise the thermal stability of polymer matrices, elongated or flake-like shapes, tend to heat up more rapidly, leading to
leading to increased flammability. The susceptibility of NFRPCs to fire is faster combustion rates. For larger particles, the impact of heating rate
significantly influenced by the type of matrices used. Matrices prone to on devolatilization time is less significant. However, as particle size
thermal degradation may result in unsatisfactory flammability re­ increases, the influence of particle shape becomes more pronounced due
sponses, as they can disintegrate when exposed to heat, releasing smoke to the predominance of internal heat transfer mechanisms within larger
and volatile substances. Therefore, carefully selecting matrices in particles. Near-spherical particles, for example, typically lose mass more
NFRPCs is critical for determining their fire response slowly and produce slightly lower volatile yields than flake-like or cy­
[125,129,137,138]. lindrical particles. This effect becomes more evident with increasing
In specific conditions, a phenomenon known as the ‘scaffolding ef­ particle size, as particles with lower length-to-diameter (L/D) ratios
fect’ can occur. This effect involves the fibre reinforcement in a com­ exhibit reduced devolatilization and burnout times [141,145].
posite material, preventing the molten degradation by-products of the In the case of natural plant-based fibres, particle morphology plays a
polymer from directly interacting with the heat source. Consequently, crucial role in determining flammability. Fibres with shapes that pro­
this process can potentially enhance the material's resistance to heat mote a higher surface area relative to their volume are more susceptible
[125]. However, when integrating natural fibre reinforcements, the to ignition due to their faster heating rates. This increased susceptibility
thermal stability of polymer matrices is often compromised, leading to can result in more severe fire hazards. Therefore, accurately assessing
increased flammability. This compromise is attributed to the fibres' the flammability and explosibility of dust necessitates careful consid­
tendency to absorb moisture due to their pendant hydroxyl and polar eration of particle shape alongside size. By defining and standardizing
groups, resulting in weak interfacial bonding between the fibre and the specific parameters for particle size and shape, researchers and industry
hydrophobic matrix polymers. The concentration of fillers within the professionals can develop more effective strategies for reducing the risks
matrix can also influence the final properties of NFRPCs, including their associated with the flammability of natural fibres. This includes
flammability [139,140]. Therefore, meticulously considering these designing safer applications, optimizing fibre processing techniques,
factors is essential during the design and fabrication of NFRPCs. The and implementing appropriate fire prevention measures to enhance
selection of matrices in NFRPCs significantly impacts their flammability, safety across various industries.
emphasizing the need for thoughtful material selection and composite
design. 3.5. Fibre reinforcements

3.4. Particle size and shapes The flammability of NFRPCs is a complex interplay of various factors,
each contributing to the overall fire behaviour of these materials. One of
Fibre particle size and shape are critical parameters that significantly the key determinants is the concentration of fibres within the composite.
determine solid particles' physical and chemical behaviour, particularly For instance, an intriguing phenomenon is observed in Polypropylene
concerning flammability and dust explosions. These factors are (PP) composites when the flax fibre concentration exceeds 30 %. This

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

increase leads to a notable reduction in both the HRR and Mass loss rate Halogen-free flame retardants (HFFRs) are often used to promote char
(MLR), resulting in a shorter burning time [138,146]. This underscores formation and are referred to as such as PP and PE) ‘enhance’ fire
the significant influence of fibre concentration on the composite's fire resistance flame retardant (IFR) systems. The term “intumescence”
resistance properties. comes from the Latin “intumescere,” meaning to swell [156]. When
The type of fibre and matrix material also play a crucial role in exposed to high temperatures, intumescent materials expand and form a
shaping the burning rates. For instance, epoxy composites reinforced protective char layer on the surface. This layer acts as an insulating
with flax fibres tend to exhibit higher HRRs and burning rates than their barrier, limiting oxygen supply to the combustion site and protecting the
glass-epoxy counterparts. This highlights the importance of judicious material from direct heat and flame exposure.
selection of fibre and matrix materials in managing the flammability of Intumescent flame retardants (IFRs) are widely recognized for their
NFRPCs. Adding another layer of complexity, certain fibre-matrix effectiveness in enhancing the fire resistance of polymers. The charred
combinations, such as wood-PP composites, have ignited more rapidly layer they produce serves as a protective shield between the heat source
than pure PP samples. This occurs despite their reduction in MLR, HRR, and the polymer, preventing further combustion and reducing the risk of
and toxic gas emissions [113–115], underscoring the intricate balance material dripping during a fire. Modern IFR technologies primarily
between different factors in determining ignition time. utilize halogen-free flame retardants (HFFRs), which are considered
environmentally safer because they do not degrade into harmful by-
3.6. Flame retardants and interfacial bonding between the fibre and products like dioxins. Halogen-based flame retardants, particularly
polymer matrix those containing aromatic rings, can break down into toxic compounds
such as chlorinated dioxins, classified as highly hazardous under the
There are two primary strategies to enhance the flame resistance of Stockholm Convention on Persistent Organic Pollutants. In contrast,
natural fibre-reinforced polymer composites: incorporating flame re­ HFFRs offer a safer alternative by promoting stable char formation
tardants into the polymer matrix and modifying the fibre surface with without releasing harmful substances during combustion.
flame-resistant agents such as functional groups or particulate additives [97,147,156,157]. The mechanism by which IFRs work, involving the
[147]. In both approaches, the fibre-matrix interface plays a key role in expansion and protective action of the char layer, is illustrated in Fig. 2.
determining the composite's overall performance, including its me­ The effectiveness of flame-retardant materials depends on the type of
chanical properties [147,148]. Flame retardants are essential in retardant used and the manner in which they are integrated into the
reducing material flammability by interfering with the combustion composite structure. Among the various options, ammonium poly­
process. They are broadly classified into two categories based on their phosphate (APP) stands out as a leading intumescent flame retardant. Its
mechanisms: reactive and additive [149,150]. ability to form a robust char layer when exposed to heat makes it a
Reactive flame retardants chemically bond with polymer chains reliable protective barrier against fire. The intumescent behaviour of
during polymerisation, providing permanent fire resistance without APP is characterized by its thermal decomposition at elevated temper­
significantly affecting the material's physical properties. This chemical atures, leading to the release of phosphoric acid. This acid catalyzes the
bonding prevents the flame retardants from migrating or volatilising dehydration of the polymer matrix, promoting the formation of a
over time, ensuring consistent performance. Reactive flame retardants carbonaceous char that expands and insulates the underlying material
often include thermally stable compounds such as phosphorus-based from heat and oxygen, thereby inhibiting flame spread [158–160] The
substances, metals, boron, polyhedral oligomeric silsesquioxanes, and char layer not only acts as a thermal barrier but also reduces the release
melamine derivatives. Modifying polyols with flame-retardant elements of flammable gases, contributing to the overall flame retardancy of the
and reactive groups also improves compatibility within polymer sys­ composite material [161,162]. However, one of the significant chal­
tems. Phosphorus, silicon, and nitrogen-containing monomers are lenges associated with its use is the reduction in mechanical properties
commonly used in polyurethane synthesis for their superior flame- of the resulting composites. This reduction can be attributed to several
resistant properties [149,151,152]. Additionally, ongoing research fo­ factors, including the high loading levels of APP required for effective
cuses on the synergistic effects of combining reactive and additive flame flame retardancy, its poor compatibility with various polymer matrices,
retardants to enhance the overall fire safety of materials. and the physical and chemical interactions that occur during processing.
Additive flame retardants, on the other hand, are incorporated into Protein-based flame retardants from soy, casein, and keratin are
polymers through physical blending, a popular method due to its gaining attention as eco-friendly alternatives, offering effective fire
simplicity and efficiency. However, this approach poses challenges. resistance while promoting sustainability in materials science. Soy
Inorganic flame retardants often have poor dispersion within the poly­ protein isolate (SPI) has been explored as a promising candidate for
mer matrix, necessitating surface modifications to improve compati­ flame retardancy due to its inherent properties. Recent studies have
bility and uniform distribution. While organic flame retardants disperse
more easily, they can migrate within the material over time, reducing
their long-term effectiveness. Achieving the desired flame retardancy
often requires high concentrations of additives, which can lead to
further issues with dispersion and migration. Moreover, using large
quantities of additives can negatively affect other material properties,
such as mechanical strength and durability [150,153]. Unlike reactive
flame retardants, additive flame retardants do not form chemical bonds
with the polymer, and excessive use can compromise material perfor­
mance [154]. Some flame retardants release non-flammable gases, such
as water vapour and carbon dioxide, which dilute the fuel, cool the
polymer, and leave behind a protective char layer.
Char formation is a critical mechanism for enhancing fire resistance
in flame-retardant materials. When polymers combust due to thermal-
oxidative reactions, they release volatile compounds that sustain com­
bustion. Flame retardants can be designed to reduce the emission of
these volatile substances and promote the formation of a protective char
layer on the material's surface. This char suppresses smoke and dissi­
pates heat, creating an effective flame-retardant barrier [147,155]. Fig. 2. Fire protection mechanism of intumescent flame retardants.

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

demonstrated that SPI can be combined with other materials, such as matrices, thereby improving interfacial bonding [173]. These modifi­
sisal cellulose microcrystals and graphene, to create hydrophobic, cations not only enhance mechanical properties but also reduce mois­
flame-retardant composite films. These composites exhibit enhanced fire ture absorption, which is crucial for maintaining composite integrity in
resistance while maintaining flexibility and mechanical integrity, mak­ humid conditions [174].
ing them suitable for applications in fireproof packaging and sensor Flammability remains a critical concern in the use of natural fibres in
materials [163] .The incorporation of SPI not only improves the flame composites. The incorporation of flame retardants, such as ammonium
retardancy but also contributes to the overall biodegradability of the polyphosphate (APP), can significantly reduce flammability, although
material, addressing environmental concerns associated with conven­ the effectiveness of these additives can vary based on the type of fibre
tional flame retardants [164]. and polymer matrix used [115,175]. Furthermore, treatments that
Similarly, casein-based flame retardants have shown remarkable improve fibre-matrix adhesion can enhance fire performance by creating
effectiveness in enhancing the flame resistance of cotton fabrics. a more stable composite structure that resists ignition [176]. Thermal
Research indicates that casein-derived flame retardants, which are properties in natural fibre-polymer composites are intricately linked to
halogen-free and contain phosphorus and nitrogen, can significantly interfacial bonding. Poor adhesion between fibres and the polymer
increase the limiting oxygen index (LOI) of treated fabrics, thereby matrix can result in thermal degradation during processing, as ineffec­
improving their flame-retardant performance [165]. The mechanism tive heat transfer within the composite compromises its stability [176].
behind this effectiveness is attributed to the formation of a char layer Enhancing interfacial bonding through surface treatments improves
during combustion, which acts as a barrier to heat and flame propaga­ thermal stability, enabling composites to withstand higher processing
tion. This char formation is crucial for reducing flammability and temperatures without significant degradation [115,177]. Additionally,
enhancing the thermal stability of the treated materials [166]. the unique morphology of natural fibres provides inherent thermal
Furthermore, keratinous materials, such as those derived from insulation, offering advantages in specific applications.
chicken feathers, have been investigated for their flame-retardant Interfacial bonding is equally critical in maintaining the mechanical
properties. The unique structure of keratin, which contains numerous and fire-resistant properties of flame-retardant composites. Strong
polar groups, contributes to its high thermal stability and char-forming bonding ensures efficient stress transfer between the matrix and fibres,
ability. This makes keratin-based flame retardants effective in inhibiting preserving mechanical integrity under thermal stress during combus­
the decomposition of treated materials at elevated temperatures, thus tion. This robust interface also stabilizes the char layer, a vital compo­
enhancing their flame resistance [166]. The use of such natural proteins nent in fire resistance. A stable char layer inhibits flame propagation,
not only provides a sustainable option but also leverages waste mate­ minimizes crack formation, and prevents heat penetration into the
rials, promoting a circular economy in material production. In addition material. Conversely, weak bonding leads to discontinuous char layers,
to the inherent properties of these proteins, the development of novel creating thermal weak spots that reduce the material's effectiveness as a
formulations that combine various bio-based components is a growing fire barrier. Uneven fibre dispersion further exacerbates these issues,
area of research. For instance, the combination of phytic acid with causing localized burning and diminished fire resistance [178–183].
amino acid salts has been shown to create effective flame-retardant Thus, optimizing the fibre-matrix interface is essential to enhance fire
systems for polypropylene, highlighting the versatility of bio-based retardancy without compromising the material's mechanical properties.
flame retardants in different polymer matrices [167]. The synergistic As shown in Table 2, flame retardants can be categorized into six
effects of combining different bio-based flame retardants can lead to groups based on their chemical composition: mineral, halogenated,
improved performance, making them suitable for a wider range of phosphorus-based, nitrogen-containing, silicon-based, and MWCNT-OH
applications. (multi-walled carbon nanotubes with hydroxyl functional groups). Each
category is suited to specific industrial applications, offering distinct
3.6.1. Interfacial bonding between the fibre and polymer matrix fire-retardant mechanisms and performance characteristics. For
A key factor influencing the performance of natural fibre-reinforced example, mineral flame retardants, such as metal hydroxides and bo­
polymer composites is the interfacial bonding between the fibres and the rates, are commonly used in plastics and textiles. In contrast, haloge­
polymer matrix. Weak fibre-matrix interactions can compromise the nated flame retardants, which contain halogen atoms, are frequently
char's integrity, while uneven fibre distribution may create localized applied in electronics and furnishings. Phosphorus-based flame re­
weak points or hotspots during combustion, undermining fire protec­ tardants are widely used in polymers, nitrogen-containing retardants are
tion. At higher flame retardant loadings, improved char formation, heat typically incorporated into high-impact polystyrene, and silicon-based
absorption, and oxygen depletion can enhance fire resistance [168,169]. flame retardants are prized for their application across various in­
However, achieving this balance is critical, as excessive flame retardant dustries. The sixth category, MWCNT-OH, has gained popularity in
content can adversely impact the composite's mechanical properties. epoxy nanocomposites due to its exceptional fire-resistant properties.
The integration of natural plant-based fibres, particularly cellulosic fi­ Understanding these categories is crucial, as each type of flame
bres, into polymer matrices is influenced by several factors related to retardant is engineered to meet the specific demands of various in­
interfacial bonding. These factors significantly affect the mechanical dustries. For instance, mineral-based flame retardants play a key role in
properties, flammability, and thermal stability of the resulting com­ textile manufacturing. However, halogenated flame retardants, while
posites. The inherent hydrophilic nature of natural fibres contrasts with effective at inhibiting flames, raise environmental concerns due to the
the hydrophobic characteristics of most polymer matrices, leading to potential release of toxic by-products like dioxins. Phosphorus- and
challenges in achieving effective interfacial bonding. This in­ nitrogen-based retardants provide a more environmentally friendly
compatibility often results in poor adhesion, which can diminish the alternative, with growing interest in halogen-free flame retardant sys­
mechanical performance of the composites and increase their suscepti­ tems. Silicon-based flame retardants are valued for their versatility and
bility to moisture absorption, thermal degradation, and flammability wide range of applications. The use of MWCNT-OH in epoxy nano­
[170,171]. composites reflects ongoing advancements in flame retardancy,
To address the issues associated with poor interfacial bonding, combining superior fire resistance with enhanced material performance.
various surface modification techniques have been developed. Alkaline Achieving optimal fire resistance in flame-retardant materials re­
treatments can enhance fibre surfaces by removing hemicellulose and quires selecting the right flame retardant and ensuring proper interfacial
lignin, which increases surface roughness and improves adhesion to the bonding and uniform fibre dispersion within the polymer matrix. These
polymer matrix [172]. The application of coupling agents, such as ma­ factors are critical for maintaining both the material's structural integ­
leic anhydride grafted polypropylene (MAPP), has proven effective in rity and its fire resistance. Tailoring the flame retardant to the specific
enhancing compatibility between hydrophilic fibres and hydrophobic material and application is essential to balancing fire protection,

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

Table 2
Comprehensive overview of flame retardants: characteristics, applications, toxicological impacts, and regulatory status.
Type of Flame Description Nature/Properties Applications Toxic effects Regulatory Status Ref.
Retardant /(Partial Ban)

Mineral Flame Comprise They are typically Used in plastics and Mineral flame Mineral flame [181–188]
Retardants compounds like additive and can textiles. retardants, such as retardants are not
(Based on metal metal hydroxides, endothermically aluminium hydroxide typically subject to bans
hydrates, hydroxyl decompose at certain (ATH) and magnesium or severe restrictions
particularly carbonates, and temperatures. hydroxide (MDH), are due to their low toxicity
aluminium and borates. considered to be and environmental
magnesium relatively non-toxic impact. However, there
hydroxide) compared to other are regulations to
types of flame control exposure to dust
retardants. However, during manufacturing
they can cause and handling.
irritation to the skin,
eyes, and respiratory
tract when in dust
form.
Halogenated Flame Contain halogen They can be either Used in furnishings, Halogenated flame Due to their persistence [181–183,186,189–193]
Retardants atoms and act as reactive or additive. electronics, and retardants can release and toxicity,
(Brominated and effective flame Most halogenated electrical devices. toxic gases like dioxins halogenated flame
chlorinated inhibitors. flame retardants are and furans during retardants have been
compounds) used in conjunction combustion. These partially banned or
with a synergist to compounds are restricted in several
enhance their harmful to human countries, including the
efficiency. health and the European Union and
environment and can the United States.
cause cancer,
endocrine disruption,
and neurological
damage.
Phosphorus-based Encompass They can be either Used in typical Some phosphorus- Certain phosphorus- [181–183,186,194,195]
Flame Retardants phosphorus reactive or additive. polymers to improve based flame retardants based flame retardants
(Compounds of compounds They prevent the their flame can release phosphine face restrictions due to
phosphorus) known for their growth of fire or inhibit retardancy. gas during combustion, their potential health
fire-retardant the combustion of which is highly toxic risks, although they are
properties. polymeric substrates. and can cause severe generally considered
respiratory issues. safer than halogenated
alternatives.
Nitrogen- Include inhibitors They contribute to the Used in high-impact These compounds can Certain nitrogen-based [181–183,191,196,197]
containing Flame with nitrogen- formation of char that polystyrene. produce toxic nitrogen flame retardants, such
Retardants containing swells and foams oxides (NOx) during as melamine cyanurate,
(Melamine and functional groups. during combustion. combustion, which can are under scrutiny due
Melamine cause respiratory to concerns over
cyanurate) problems and potential health effects.
contribute to air Regulations and
pollution. restrictions vary by
country, with some
regions implementing
partial bans.
Silicon-based Flame Contain silicon as They form a vitrified Used in civil Silicon-based flame These flame retardants [181–184,198,199]
Retardants a key element and layer on the polymer engineering, retardants are are not commonly
(Silicone- are valued for surface during construction building, generally considered banned but may be
containing their fire-resistant combustion, which electrical, less toxic than other regulated depending on
polymeric characteristics. effectively hinders the transportation, types, but specific their specific
materials) transfer of oxygen, aerospace, defence, formulations can vary applications.
heat, and mass. textiles, and cosmetics in their effects.
industries.
MWCNT-OH Flame MWCNT-OH They can significantly Used in epoxy Inhalation of carbon MWCNTs are regulated [200–204]
Retardants (Multi-Walled reduce the number of nanocomposites. nanotubes can cause due to their potential
(Multi-walled Carbon conventional flame lung damage and health risks, especially
carbon nanotubes Nanotubes) are retardant additives, inflammation, and in occupational
functionalised by used as flame making the material concerns about their settings.
hydroxyl) retardants. with optimal flame long-term health
retardant properties. impacts exist.

mechanical performance, and environmental impact. This integrated due to the release of toxic gases like dioxins during combustion, which
approach enables industries to enhance fire safety while meeting regu­ has led to partial bans in many regions. Phosphorus-based and nitrogen-
latory standards and performance requirements for various applications. based flame retardants provide safer alternatives, but they are not
The analysis of various flame retardants highlights the delicate bal­ without issues. They can release toxic gases, such as phosphine and ni­
ance between their effectiveness and potential health and environ­ trogen oxides, which present respiratory hazards and environmental
mental risks. Mineral flame retardants, such as aluminium and concerns.
magnesium hydroxide, are non-toxic and therefore safer compared to The increasing use of silicon-based flame retardants signals a shift
other types, but they can be less efficient in fire protection. Halogenated toward less toxic solutions, though challenges remain in optimizing their
flame retardants, though highly effective, pose significant health risks performance and managing higher costs. Meanwhile, MWCNTs show

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

great potential for enhancing flame resistance with minimal additive 3.62 % in impact strength are observed. This improvement is attributed
use, but their potential health risks, particularly through inhalation, to good interfacial bonding between the alkylammonium ion groups of
necessitate strict regulatory oversight. Overall, the regulatory landscape the nano clay and the matrix and improved surface roughness and
is evolving to address the trade-off between fire safety and toxicity, adhesion of the sisal fibres. Subasinghe et al. [213] report different
driving innovation in the development of safer and more sustainable findings when halloysite nanotubes (HNT) and montmorillonite nano­
flame retardants. The push for less harmful solutions is reshaping the clay (MMT) (3 wt%) are added to a polypropylene matrix with kenaf
industry, emphasizing both enhanced fire protection and reduced bast fibres (30 wt%). The tensile strength decreases by 19.3 % and 9.2 %,
environmental impact. flexural strength drops by 11.31 % and 25.99 %, and impact strength
reduces by 34.6 % and 39.3 % for HNT and MMT, respectively. This
3.6.2. Flame retardants affect the mechanical properties of natural fibre decline is likely due to the flame retardants interfering with interfacial
Incorporating flame retardants into polymer composites reinforced stress transfer, and the nucleating effect of HNT and MMT may alter the
with natural fibres can significantly alter mechanical properties such as crystallinity of the matrix, negatively affecting mechanical properties.
tensile strength, tensile modulus, flexural strength, flexural modulus, In a study by El-Sabbagh et al. [96] the combination of aluminium
and impact strength. The nature of these changes, whether improve­ trihydroxide, zinc borate, and ammonium polyphosphate (60 wt%) with
ments or reductions, depends on the type of flame retardant, fibre, and flax fibres (30 wt%) in a polypropylene matrix leads to a 35 % decrease
matrix used in the composite. These effects are driven by the interfacial in tensile strength but a 46 % increase in tensile modulus. The reduction
interactions between the fibres, matrix, and flame retardant additives, in elongation lowers the impact properties, and the high shear rate
which collectively influence the composite's overall structural integrity during processing may damage the natural fibres, further contributing to
and performance. Understanding these interactions is essential for the reduced mechanical performance. Szolnoki et al. [214] found that
optimizing the mechanical behaviour of flame-retardant composites for when phosphoric acid and amino silane (8 wt%) are used with hemp
specific applications. fibres (30 wt%) in an epoxy matrix, tensile strength and flexural strength
The mechanical properties of polymer composites are often decrease by 2.2 % and 5.7 %, respectively, while tensile modulus and
compromised when high concentrations of APP are added. For instance, flexural modulus increase by 20.85 % and 5.9 %. These changes suggest
studies have shown that the addition of APP can lead to a decrease in that while strength is slightly compromised, the stiffness and resistance
tensile strength and impact toughness in materials such as polyurethane to bending are improved, likely due to strong fibre-matrix bonding
and epoxy resins [205,206]. The mechanical degradation is particularly without fibre pull-outs or delamination.
pronounced when APP is used in its conventional powder form, which Yu et al. [215] propose a more environmentally friendly approach
can lead to poor dispersion and phase separation within the polymer using biobased electrolytes, such as cationic chitosan, anionic phytic
matrix, resulting in weak points that are susceptible to failure under acid, and a flame-retardant cationic electrolyte melamine (20 wt%),
stress [206,207]. This phenomenon is exacerbated in systems where APP with ramie fibres (52 wt%) in an unsaturated polyester matrix. How­
is not adequately modified or encapsulated to enhance its compatibility ever, this combination results in a 7.7 % decrease in tensile strength and
with the polymer [208]. Moreover, the moisture sensitivity of APP can an 8 % reduction in flexural strength. These reductions may stem from
further contribute to the reduction of mechanical properties. APP tends the hydrolysis of the natural fibre by the acid at lower temperatures.
to exude from the polymer matrix under humid conditions, leading to a Introducing Fe+ 3 treatment could potentially mitigate the catalytic
loss of flame retardant efficacy and a subsequent decline in the me­ degradation caused by phytic acid, reducing the adverse effects on
chanical integrity of the composite [206]. This issue is particularly mechanical properties. In a similar study by Chu et al., [216] adding
critical in applications where the material is exposed to varying envi­ phosphorus- and nitrogen-containing silane coupling agents (10 wt%)
ronmental conditions, as the leaching of APP can compromise both its with ammonium polyphosphate to a ramie fibre (49.7 wt%) and un­
flame retardant properties and the structural performance of the saturated polyester composite results in a 10.13 % decrease in tensile
polymer. strength. This decrease is due to the enhanced surface roughness of the
To address these challenges, researchers have explored various fibres, which improves adhesion and interfacial bonding but does not
modification techniques to improve the compatibility of APP with prevent the reduction in tensile strength. The rougher surface increases
polymer matrices. For example, microencapsulation of APP has been adhesion, contributing to better interfacial interlocking, although the
shown to enhance its dispersion and reduce its negative impact on me­ overall tensile performance remains compromised.
chanical properties. By encapsulating APP in a polymer shell, the Khalili et al. [165] demonstrate that combining zinc borate and
interaction between APP and the polymer matrix can be improved, ammonium polyphosphate (5 wt% + 10 wt%) as flame retardants with
leading to better mechanical performance while still achieving effective palm oil fibres (20 wt%) in an epoxy matrix leads to reductions in me­
flame retardancy [208]. Additionally, the use of synergistic agents, such chanical properties. Specifically, the study observes a 2.5 % decrease in
as melamine or expandable graphite, in combination with APP has been flexural strength, a 16.8 % reduction in flexural strain, a 20 % drop in
investigated to enhance both flame retardancy and mechanical proper­ ultimate tensile strength, and a 14 % reduction in elongation at break.
ties, demonstrating that careful formulation can mitigate some of the The use of ultrasonic dispersion and vacuum resin infusion methods
adverse effects associated with APP [209,210]. affects fibre dispersion and fibre-matrix interaction, contributing to the
According to Guo et al. [211] using boric acid as a flame retardant overall decline in mechanical performance. These findings highlight that
(30 wt%) in bamboo fibre (22 wt%) and epoxy matrix composite results the integration of flame retardants into natural fibre-reinforced polymer
in an 8.18 % reduction in tensile strength, a 2.89 % reduction in tensile composites significantly impacts their mechanical properties. Whether
modulus, and a significant 76.6 % increase in impact strength. The these effects result in improvements or reductions depends on the spe­
reduction in tensile properties is likely due to boric acid species on the cific flame retardant, fibre, and matrix used. For instance, some flame
fibre surfaces restricting interfacial interactions, weakening the com­ retardants, such as boric acid and nano clay, can enhance impact
posite's ability to bear tensile loads. However, the increased impact resistance and tensile properties. In contrast, others, like halloysite
strength suggests better energy absorption during sudden impacts due to nanotubes and montmorillonite, may reduce strength and modulus by
the altered fibre-matrix bonding. disrupting interfacial stress transfer. These variations underscore the
In contrast, the research by Paluvai et al. [212] shows that adding complex interactions between a composite's components, emphasizing
nano clay and Bis (2-hydroxy-ethyl) methyl tallow ammonium (1 wt%) the importance of carefully selecting materials and processing tech­
to sisal fibres (30 wt%) in an epoxy matrix enhances the mechanical niques. Understanding these interactions is crucial for optimizing flame-
properties. Increases of 7.56 % in tensile strength, 12.75 % in tensile retardant composites to meet specific mechanical performance
modulus, 6.11 % in flexural strength, 2.72 % in flexural modulus, and requirements.

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

3.6.3. Modeling fire resistance in plant fibre-polymer composites for their eco-friendly nature and ability to enhance fire safety in NFRPCs
The modeling of fire resistance in plant fibre-polymer composites is a [151,224,225].
complex yet crucial area of research, driven by the need to enhance Additionally, metallic oxide particles are effective as additives,
material performance in fire-critical applications. Advanced models improving char residues' thermal stability and morphological structure,
incorporating pyrolysis and combustion sub-processes are critical to thereby contributing to the material's overall flame retardancy. These
address these complexities. For instance, Dutta et al. [217] developed a nanoscale additives are particularly valued for their eco-friendliness and
coupled transient heat transfer finite element model to predict the efficiency in reducing heat release rates and mass loss rates, even at low
temperature distribution in flax-PP composite beams during fire expo­ loading levels. Overall, flame nanometric particles play a crucial role in
sure. The model effectively captures key thermal phenomena by developing advanced flame-retardant materials by providing high flame
combining finite volume and finite element methods and applying heat resistance, enhancing safety, and maintaining the performance of
flux boundary conditions from the Fire Dynamics Simulator (FDS) in polymers and textiles. Various studies and ongoing research endeavours
ABAQUS. Importantly, this work highlights the need to incorporate support these particles' effectiveness and applications to explore their
decomposition sub-models, such as pyrolysis and char formation, to full potential in flame retardancy [226–229].
improve accuracy. These adjustments enable more precise temperature Polymeric and textile-based materials encounter limitations related
distribution, HRR, and structural damage predictions, essential for to flammability risks and thermal stability. To mitigate these challenges,
optimizing these materials in applications requiring high fire resistance. flame retardant materials are introduced as fillers within polymer
Building on this foundation, Tran et al. [218] presented a three- matrices or applied as coatings on textiles, aiming to enhance fire safety
dimensional finite element model to analyse the thermomechanical and thermal resilience. Kavimani et al. [230] examined the utilization of
behaviour of flax chipboard panels during fire exposure. This model montmorillonite (MMT) nanofillers and graphene oxide reduced (GO-r)
integrates kinetic pyrolysis sub-models alongside anisotropic plasticity nanoclay as reinforcing agents in hybrid epoxy-based nanocomposites.
and continuum damage mechanics, implemented via ABAQUS user Incorporating these nanofillers enhanced compressive strength,
subroutines. Validation through simulations aligned with various fire modulus of rupture, toughness, and non-ignition timing. However,
tests confirmed the accuracy of temperature predictions under different beyond a filler content of 0.3 %, material strength exhibited a decline.
moisture contents, demonstrating that models must account for these Notably, the study identified a ductile failure mechanism attributed to
variables. However, discrepancies in panel displacement predictions the combined presence of these fillers.
after prolonged fire exposure underscore the need for further refinement Graphene, characterized by its two-dimensional sp2-hybridised
in thermomechanical coupling and combustion effects. structure, emerges as a promising carbon nanomaterial. This compre­
Moreover, Pope et al. [219] investigated the thermal behaviour of hensive review encompasses traditional flame retardants, diverse
laminated bamboo samples under various radiant heat fluxes (5, 10, 30, methods for synthesizing graphene layers, and the potential application
and 60 kW/m2), revealing significant distinctions based on the orien­ of graphene sheets as standalone flame retardants for polymeric mate­
tation of heating—parallel versus perpendicular to the grain. Moisture rials. Comparative analysis with other commonly used nanofillers
migration, particularly when bamboo is heated parallel to the grain, highlights graphene's role in augmenting flame retardancy in polymers
enhanced convective heat transfer, leading to deeper heat penetration and textiles. Furthermore, the study explores synergistic flame retardant
and more pronounced endothermic effects at around 100 ◦ C. These effects achieved by incorporating nanoparticles onto graphene sheets in
findings emphasize the need for fire models to incorporate both polymer nanocomposite [231]. The impact depends on the type of
convective heat transfer and moisture migration effects, particularly for nanoparticles and varies based on the composite composition. Addi­
fibres that experience variable responses to heat depending on their tionally, understanding the quantity of nanoparticles used is crucial for
internal structure. achieving the desired balance between fire resistance and mechanical
Retarding mechanisms, such as enhanced char formation and flame- properties.
retardant treatments, are essential in improving fire resistance. The
models must reflect the adjustments in material chemistry and proper­ 4. Types of flammability testing techniques
ties resulting from these mechanisms, allowing for more precise simu­
lation of fire retardation processes. For example, fibres treated with Based on specific testing requirements, various materials are sub­
chemical retardants may produce a more stable char layer, slowing heat jected to flammability tests. These tests utilize a Bunsen burner and are
propagation and combustion. Incorporating these mechanisms into fire conducted in either a vertical or horizontal configuration, depending on
models allows for improved predictions of heat release, thermal con­ the material's nature and the test protocol's specifics. Various aspects of
ductivity, and the overall performance of fibre polymer composites the material's response to the flame are meticulously examined in a
under fire conditions. vertical flammability test. These include the duration for which the
material continues to burn after the ignition source is removed, the
3.7. Flame nano-metric particles extent of the specimen consumed by the fire, and the presence of any
flaming particles released during the process. The ASTM D635 standards
Flame nano-metric particles refer to nanoscale particles specifically play a pivotal role in evaluating the ignition and combustion charac­
engineered to enhance the flame resistance of materials. These particles, teristics of specific materials, with a particular emphasis on plastics and
often less than 100 nm in size, are incorporated into polymer matrices to polymers. Under ASTM D635, the flammability test is tailored to
improve their thermal, mechanical, and flame-resistant properties determine the burn rate of plastics with substantial wall thickness
significantly. Among the most notable are carbon nanotubes (CNTs) in [232,233]. ASTM D635 evaluates the rate and extent of the burning of
single, double, and multi-walled forms. When dispersed within the polymers and plastics in a horizontal position, serving as a critical
polymer matrix, CNTs create a network that enhances the material's standard for assessing the fire behaviour of plastic materials and
structural integrity and reduces its flammability at relatively low con­ enhancing product and structural safety. FMVSS 302 regulates the
centrations [220–222]. Another significant contributor in this domain is flammability of materials within vehicle occupant compartments,
nano clays. Nano clays, derived from layered silicate minerals, are thereby ensuring passenger safety by mitigating the rapid spread of fire
crucial in enhancing flame resistance in NFRPCs [223]. These nanoscale during accidents. ISO 3795 determines the burning behaviour of interior
particulate additives introduce polymers between their layers through materials in road vehicles, tractors, and forestry machinery, guiding
intercalation or exfoliation. While not standalone flame retardants, they manufacturers in selecting materials that reduce fire risks. UL 94 tests
significantly reduce heat release rates when combined with other flame the flammability of plastic materials used in devices and appliances,
retardants. Despite some processing challenges, nano clays are favoured ensuring compliance with fire safety criteria and contributing to overall

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

product safety by preventing fires caused by faulty or flammable ma­ methane flame is applied to the sample's lower edge, and the burning
terials [234]. and smouldering duration is recorded. The sample is exposed to the
This test holds immense value for various applications, including flame for one or two 10-s intervals to observe ignition. If the flame
quality control assessments, setting production standards, and material reaches the top clamp (125 mm), the sample fails to achieve a vertical
comparisons. The data obtained from these tests significantly influence (V) rating. The setup for the UL-94 test is depicted in Fig. 3(a).
decisions related to material selection, product design, and safety pro­ Asim et al. [245] research provides significant insights into phenolic
tocols. Manufacturers can enhance product safety and performance by composites' flammability characteristics reinforced with treated and
making informed choices based on how a material behaves when untreated pineapple leaf fibre (PALF) and kenaf fibre (KF). Utilizing the
exposed to fire. Furthermore, these tests contribute to ongoing research UL-94 test, a recognized method for assessing flame retardancy, the
and development efforts in material science, fostering the creation of study underscores the critical influence of fibre type and treatment on
advanced materials characterized by improved fire resistance. fire performance. The pure phenolic composite achieved a V-0 classifi­
To evaluate the flame retardancy of composites, a spectrum of test cation in the vertical burning test, showcasing exceptional flame resis­
techniques is utilised, ranging from bench-scale to full-scale tests in both tance due to its inherent chemical stability and low combustibility.
industrial and academic environments. These techniques include LOI However, introducing PALF, particularly untreated or at high loadings,
[120], single item burning (SBI) test [235], underwriters' laboratories raised concerns about its suitability for fire-sensitive applications. While
(UL 94) [236], NBS smoke chamber [237], Ohio State University (OSU) 40 % of PALF loading retained a V-0 classification, higher loadings (50
test [238], cone calorimeter test (CCT) [239], flame spread tests [240], % and 60 %) dropped to V-1. This decline is attributed to PALF's high
room corner test [241], and room fire test. While the ASTM D635 cellulose content, a highly flammable component. Interestingly, fibre
flammability standard remains pivotal for evaluating the combustion treatment, while enhancing mechanical properties, appeared to expose
properties of specific materials, especially plastics, it's essential to note cellulose further, exacerbating the reduction in fire resistance. These
that this standardized test quantifies the burn rate of substantial thick- findings emphasize the need to optimize treatment processes for
walled plastics. It is a valuable tool for quality control, setting produc­ balancing mechanical and fire performance.
tion benchmarks, and facilitating material comparisons. However, it's In contrast, kenaf fibre composites exhibited superior flame retard­
crucial to clarify that this test does not assess fire-related hazards. ancy, consistently achieving V-0 classifications. The inherent thermal
Instead, the ASTM D635 test provides invaluable insights into materials' stability of KF and the phenolic resins char-forming properties contrib­
ignition and combustion characteristics, playing a significant role in the uted to improved fire resistance. However, reliance on char formation
manufacturing processes of plastic products [242,243]. The systematic alone presents risks, as its effectiveness can vary with composite for­
application of flammability tests and their methodologies will be sum­ mulations and fire conditions. The horizontal UL-94 test revealed a
marised below and depicted in Fig. 3. These standards emphasize the correlation between PALF loading and combustion rates, with 60 %
commitment to safety and quality maintained within the plastics PALF showing the highest rate. Pure phenolic exhibited the lowest rate,
industry. underscoring the need for careful fibre selection and loading in fire-
The UL-94 test is a critical flammability assessment for plastics, critical applications. No dripping was observed, enhancing the com­
comprising six evaluations. The UL-94 V test uses vertically positioned posites' safety profile. Further research on thermal degradation path­
bar-shaped samples with precise dimensions (125 ± 5 mm in length and ways and fibre-matrix interactions is essential to optimize natural fibre
13.0 ± 0.5 mm in width, with a thickness up to 13 mm). A 20 mm composites for fire performance.

Fig. 3. Types of flammability testing techniques for fibres [235,244].

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

Cone calorimetry is a widely recognized method for evaluating the char layer more effectively in the vertical position. However, challenges
fire behaviour of polymers. The test involves exposing a 100 × 100 × 4 include edge effects near the sample edges and variations based on
mm3 sample to a specific heat flux (typically 10 to 100 kW/m2) using a material type. Comparing vertical results with other orientations
cone-shaped electric radiant heater. The sample is placed on a load cell comprehensively assesses material behaviour under fire conditions.
to monitor mass loss, and an electric spark initiates combustion. As the
sample burns, the reduction in oxygen concentration in the combustion 5. Mechanism of flame retardancy
gases is measured, along with CO, CO2, and smoke density. These gases
are collected through an exhaust duct system with a centrifugal fan and The mechanism of flame retardancy plays a crucial role in ensuring
hood. This procedure, standardized by ASTM E 1354 and ISO 5660, material safety by aiming to mitigate flammability and hinder the rapid
provides critical insights into the fire resistance of materials. A sche­ spread of flames. Flame-retardant materials can swiftly extinguish
matic diagram of the cone calorimeter as shown in Fig. 3(b). themselves without an external flame, halting combustion. Achieving
The M-single burning item (M-SBI) test is conducted in a dedicated flame retardancy involves disrupting the combustion cycle, which en­
fire testing room designed for such assessments. The testing apparatus compasses the interplay of fuel, heat, and oxygen. This disruption can be
consists of a robust framework that accommodates essential compo­ realised through physical, chemical, or a combination of both mecha­
nents, including the burner and test samples, as illustrated in Fig. 3(c). nisms by eliminating or reducing one or more of these essential ele­
Additional thermocouples can be placed within the panels during sam­ ments. Flame retardants encompass various chemicals that inhibit or
ple preparation for enhanced monitoring. A video camera, positioned at impede fire propagation on multiple materials. Their classification is
a 1-m distance from the panels, enables visual observation of the com­ based on their function rather than their chemical composition
bustion process. The upper section of the frame houses an exhaust duct [246,247]. The study of flame retardants holds significant importance
equipped with various sensors. Light sensors are crucial in quantifying due to their widespread presence in our environment and the potential
the smoke generated during the material's decomposition. Lastly, the health implications they may carry. This increased awareness has
exhaust duct is connected to an extraction hood, ensuring a consistent spurred efforts to understand their impact and explore the development
extraction rate of 211 cubic meters per hour. of safer alternatives [246–248]. Using flammability and thermal anal­
The Limiting Oxygen Index (LOI) quantifies the minimum oxygen ysis, researchers can deepen their understanding of materials, fostering
concentration required to sustain flaming combustion in a material, innovation in engineering and material science development.
expressed as a volume percentage (vol%). Introduced by Fenimore and
Martin in 1966, LOI is a crucial measure of material flammability. 5.1. Fire retardancy in composites
Standards like ASTM D 2863 (U.S.), NF T 51–071 (France), and ISO 4589
(International) govern its testing. The test involves vertically placing a The fire resistance of composite materials can be bolstered by dis­
sample in a controlled oxygen‑nitrogen atmosphere, igniting it, and rupting the combustion cycle through three distinctive methods. The
determining the LOI as the oxygen concentration that sustains com­ first approach involves using specific chemicals that undergo endo­
bustion for 3 min or consumes 5 cm of the sample. thermic decomposition when heat exposure, inhibiting the composite
LOI is calculated using the equation: materials from reaching their pyrolysis temperature. The second method
employs chemicals that produce increased quantities of non-flammable
LOI = 100 × ([O2 ]/([O2 ] + [N2 ] ) (1)
by-products and char during pyrolysis. The char layer acts as a physical
Materials with LOI values below 21 % are classified as combustible, barrier, impeding heat and mass transfer between the gaseous and
while those above 21 % are self-extinguishing, indicating higher fire condensed phases. This process is commonly referred to as the
resistance. LOI is an essential screening tool in the plastics industry, condensed phase mechanism. The third approach encompasses using
though it has limitations. If melting and dripping occur during testing, flame-retardant chemicals that release a greater volume of non-
LOI values can decrease with rising temperatures, and materials may flammable gases during combustion, reducing the oxygen concentra­
exhibit misleadingly high LOI values. Moreover, LOI can underestimate tion within the flame zone and acting as a flame retardant [249–251].
the fire resistance of nanocomposites, where surface flame spread may
not reflect the material's overall resistance. Despite these limitations, 5.2. Flame retardant strategies
LOI remains a valuable indicator of material flammability. Fig. 3(d)
shows the Limiting Oxygen Index setup. Enhancing the fire resistance of composite materials requires a
The Ohio State University (OSU) method is a robust technique for comprehensive approach involving various strategies to impede or
assessing the Rate of Heat Release (RHR) during forced flaming com­ obstruct the combustion process, thereby reinforcing the materials'
bustion of diverse materials and products. This method involves con­ ability to resist fire. There are three distinct approaches to achieving this
current heat and smoke release measurements, with a specimen objective. The first strategy involves incorporating specific chemicals
positioned within a controlled exposure chamber. These measurements that undergo an endothermic reaction when exposed to heat. This re­
span from the ignition phase to the completion of the test, as depicted in action prevents the temperature from reaching the pyrolysis threshold of
Fig. 3(e). It highlights the effects of sample thickness, char formation, the composite materials, effectively inhibiting combustion. The second
and orientation. Vertical positioning influences flame spread, smoke strategy employs chemicals that generate more non-flammable by-
production, and heat transfer, offering comprehensive fire behaviour products and char during pyrolysis. The resulting char layer acts as a
insights. critical physical barrier, impeding the transfer of heat and mass between
Despite these challenges, advancements in this dynamic field the gaseous and condensed phases, known as the condensed phase
continue to provide intriguing insights into the flammability charac­ mechanism. The third strategy, the gas phase mechanism, utilizes flame-
teristics of a wide range of materials. The vertical positioning of mate­ retardant chemicals that release more non-flammable gases during
rials during fire testing, such as in the OSU test, has significant combustion. This process reduces the oxygen concentration within the
implications. When a sample is oriented vertically (perpendicular to the flame zone, effectively acting as a flame-retardant agent. Collectively,
heat source), several effects come into play. Flame spread predomi­ these strategies offer a comprehensive approach to enhancing the fire
nantly occurs upward, influenced by the material's surface and edges. resistance of composite materials, paving the way for potential ad­
Additionally, smoke generation is affected; smoke rises more efficiently vancements in safety and material engineering [225,249–251].
due to buoyancy, impacting visibility and evacuation. Vertical posi­
tioning also influences the material's heat transfer mechanisms (con­
duction, convection, and radiation). Some materials form a protective

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5.3. Flame-resistant treatments for strengthening fibres composite structure with a lignin matrix, hemicellulose, and cellulosic
micro-fibrils, where the micro-fibrils serve as the primary load-bearing
Synthetic and natural fibres are intentionally integrated into poly­ component [91,140,270,271]. Hemicellulose predominantly in­
meric matrix systems to enhance their mechanical strength to fulfill fluences these fibres' thermal and biological degradation properties,
diverse application requirements. In an era emphasizing environmental while the combination of lignin and hemicellulose impacts their flame
responsibility, there's a concerted effort to prioritize biodegradable degradation properties. As a result, investigating these natural fibre
natural fibres whenever feasible, aligning with sustainable practices materials' flammability and flame retardancy has become a significant
[72,252,253]. Unlike synthetic fibres such as glass, carbon, and ceramic, area of study.
which inherently possess flame-retardant properties, natural fibres are Sherwani et al. [272] conducted a comprehensive flammability
highly flammable, burning rapidly and releasing heat, light, and smoke. analysis on untreated and treated Sugar Palm Fibre (SPF)/PLA com­
Fibres like flax, jute, bamboo, sugar palm, ramie, coir, sisal, and others posites, employing the UL-94 horizontal burning test according to ASTM
commonly used as reinforcing agents in polymeric composites pre­ D635. The test ignited the sample using a natural gas flame, recording
dominantly comprise lignocellulosic materials, showcasing significant the time it took for the flame to travel between two marks (25 mm and
compositional diversity. However, treating these lignocellulosic natural 100 mm from the sample's end). The vertical burning rate test applied
fibres with suitable flame-retardant chemicals can mitigate their flam­ the flame to the sample's bottom in two 10-s intervals.
mability, making them a safer choice across a wide range of The flame retardancy of the composite materials was assessed under
applications. the UL-94 standard in a horizontal orientation. Summarised results in
Imparting flame-retardant properties to natural fibres can be ach­ Table 4 show that all treated SPF and PLA composites exhibited excel­
ieved through three distinct techniques: i) The Pad-Dry-Baking tech­ lent flame-retardant characteristics, maintaining notably low burning
nique, ii) The Spraying-Baking technique, and iii) The Steeping-Drying rates. Notably, the 6 % alkaline-treated SPF composite burned at a rate
technique. Flame-retardant agents are classified based on factors like of 27.64 mm/min, whereas the untreated composite burned at 53.51
chemical structure, the principle of flame retardancy, and the durability mm/min. However, no composite burned up to 100 mm. The USP
of the finish they provide. Various conventional flame-retardant chem­ composites were extinguished within 8.97 s, reaching only 8 mm before
icals are commonly employed to enhance the flame retardancy of nat­ extinguishing. The A3 composite showed partial burning, taking 18.45 s
ural fibres, as detailed in Table 3. Regarding durability, flame-retardant and reaching 8.5 mm. The cellulose content in sugar palm fibres was
chemicals for lignocellulosic materials fall into two main types: non- observed to reduce flame retardancy due to the exposed cellulosic
durable flame retardants and durable flame retardants.

6. Fire performance of NFRPCs Table 4

Analysis of the theoretical and experimental results of alkaline-treated fibre
composites (ACF) and Raw fibre composite (RCF).
In lightweight construction, evaluating ‘fire risk’ is pivotal, consid­
ering a material or object's potential to ignite under varying conditions. Fibre loading (%) Theoretical Results Experimental results
Natural fibres, integral in this context, broadly fall into two categories. ACF RCF ACF RCF
The first group, lignocellulosic fibres—comprising materials like cotton,
30 20 19 19.3 19.1
flax, hemp, jute, sisal, ramie, and abaca—are prone to catching fire. The 20 18.7 18.5 17.5 17.3
second category consists of protein fibres such as wool, silk, leather, and 10 18.3 17.7 17.3 17.1
hair, known for their higher ignition resistance. Plant fibres encompass a 0 17.4 17.4 17 17

Table 3
Summary of different flame retardant chemicals and their mechanisms of action.
Flame Working Mechanism Examples of Flame Retardants Additional Information Chemical Nature Ref.
Retardant Type

Synergistic Flame Retardancy of the P/N, Halogen/Antimony Tri-oxide, P/ Synergistic flame retardants can enhance the Combination of [254,255]
Primary Compound Halogen flame retardancy of other compounds. For Inorganic and
Enhanced by the example, bio-based magnesium phytate and rice Organic
Presence of Another husk ash have a synergistic effect on epoxy
resins.
Intumescent Both in the Gas and Carbonizing Agent (ex-Pentaerythritol), Intumescent systems puff up to produce foams. Combination of [256–258]
condensing phase Ammonium Polyphosphate), Bowling They are used to protect combustible materials Inorganic and
Agent (ex-Melamine, Urea), Acid Donor such as plastics or wood against the attack of Organic
(ex-Phosphoric Acid heat and fire.
Metal Oxides Heat Sink Aluminium Hydroxide, Magnesium Metal hydroxides decompose endothermically Inorganic [259–261]
and Hydroxide, Alumina Trihydrate, to liberate water. They usually are smoke
Hydroxide suppressants and work predominantly in the
condensed combustion phase.
Inorganic
Boron Based Formation of Insulating Boron Phosphate, Boric Acid, Zinc Boron-based flame retardants form a Inorganic [156,262,263]
Layer Borate, Borax carbonaceous char and provide a protective
vitreous layer that strengthens and stabilizes the
char.
Phosphorus Condense Phase Tetrakis (hydroxymethyl) Phosphonium Phosphorus-based flame retardants act mainly Organic [264–266]
Based Salts THPC. in the solid phase of burning polymeric
materials and cause the polymer to char, thus
inhibiting the pyrolysis process necessary to
feed the flames.
Halogen Based Gas Phase TBPA, TCPA, Polybrominated Biphenyl Halogen-based flame retardants act directly on Organic [267–269]
Polybrominated Diphenyl Ethers, the flame, the core of the fire. They are said to
act “in the vapour phase”, meaning that they
interfere with the chemistry of the flame.

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

component after fibre treatment, resulting in decreased flame retard­ [65,276–278].

ancy [273,274]. According to Suraini et al. [276], hybrid polymeric composites were
The UL 94 burning test assessed the flame behaviour of various developed using a mix of SPF/PET fibres and epoxy resins. Various SPF
samples of SPF/PLA composites under horizontal and vertical condi­ levels (0 %, 20 %, 35 %, and 50 % by weight) were prepared, with the 0
tions. The USP sample burned completely, exhibiting a high flame, rapid % sample as the control. An epoxy and hardener mixture in a 2:1 ratio
dripping, significant smoke, and residue, with a horizontal burning rate was prepared, and Mg(OH)2 was added as an additive. The composite's
of 53.51 mm/min and an aggressive vertical burning rate of 163.04 mm/ flammability was assessed following ASTM D635 standards. The sam­
min. In contrast, samples A1 and A2 did not burn or drip but produced ple's end was exposed to a flame for 30 s during the test, and the extent of
smoke and residue, demonstrating excellent flame resistance. Sample A3 burning was measured. Cases, where the sample didn't burn were
partially burned with less residue, moderate smoke, and a horizontal recorded, while average burning rates were reported if burning
burning rate of 27.64 mm/min. Similarly, samples B1, B2, and B3 extended up to 100 mm [276,279]. Introducing sugar palm into the
showed no burning or dripping, only releasing smoke and residue. These composite increased the burning rate, with the Epoxy/PET/SPF-20
results highlight the superior flame resistance of A1, A2, B1, B2, and B3 sample showing the highest rate. However, as the SPF content
compared to the USP sample [272]. increased, the burning rate decreased, with the Epoxy/PET/SPF-35
Fig. 4(a) illustrates a visual representation of the partially burned A3 sample displaying the lowest rate at 13.25 mm/min. The study linked
sample, while Fig. 4(b) displays the unburned samples of A1, A2, and B3 char production during combustion to the reaction between magnesium
[272]. The results show that the benzoylation treatment significantly hydroxide and oxygen, serving as an additional flame retardant [276].
improves the fire resistance of natural fibres compared to the alkaline Nonetheless, the burning rate increased again in the Epoxy/PET/
treatment. The benzoylation process introduces benzoyl groups into the SPF-50 sample, indicating an SPF-to-epoxy ratio exceeding the fibre
fibres, which imparts hydrophobicity and thermal stability. It also fa­ loading that provides the best performance [276]. The study highlighted
cilitates the formation of a char layer, cross-linking within the fibre the crucial role of fibre-matrix compatibility and interfacial bonding in
structure, and modifies the chemical structure. These alterations achieving the best flame-retardant properties. Charring occurs when
enhance the strength of the fibres, their resistance to thermal degrada­ fuel loses hydrogen and oxygen during high-temperature combustion,
tion, and their overall performance under fire conditions. Conversely, leaving behind carbon. Magnesium (OH)₂, an acid and halogen-free
the alkaline treatment primarily augments the mechanical properties of flame retardant, undergoes endothermic decomposition, releasing
the fibres but does not contribute substantially to their thermal stability water to assist in flame retardation. This effect is also influenced by the
and fire resistance, unlike the benzoylation treatment. This underscores moisture present in SPF. Among the samples, the Epoxy/PET/SPF-35
the superior protective effects offered by benzoylation. (35 %) with 5 wt% PET yarn and Mg(OH)2-reinforced epoxy resin
It has been observed that a BC-treated fibre composite demonstrates showcased the most favourable SPF loading composition, as illustrated
higher thermal stability compared to an alkaline-treated fibre compos­ in Fig. 5 [276].
ite, aligning with findings consistent with Abdul et al.'s research [275]. However, despite these observations, the Epoxy/PET/SPF-35 spec­
Beyond the type of fibre used in a composite, the interfacial bonding imen exhibited superior flame retardancy compared to other specimens.
between these fibres significantly influences the composite's flamma­ This improvement was attributed to its SPF loading composition, which
bility. The UL-94 V test results for untreated and treated SPF/PLA included 5 wt% PET yarn and magnesium-reinforced epoxy resin. The
composites are provided. With the exception of the treated SPF/PLA research revealed that the flammability of these composites is signifi­
composites (excluding A3), only the USP composite showed swift igni­ cantly influenced by the SPF content. Initially, increasing the SPF con­
tion with a rapid drip. The vertical UL-94 V test demonstrated that these tent raised the burning rate, but beyond a certain threshold (35 wt% of
specimens did not burn due to the improved flame retardancy after SP SPF), the burning rate decreased, indicating an optimal fibre-to-matrix
fibre treatment. This improvement was attributed to the reduction in ratio for flame retardancy. This optimal composition, Epoxy/PET/SPF-
lignin content post-fibre treatment, decreasing from 33.24 % to 0.06 % 35, which included 35 % SPF and 5 wt% PET yarn exhibited the best

Fig. 4. (a) Partially burned (b) unburned samples [272].

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

Fig. 5. The Epoxy/PET/SPF horizontal burning rate results.

PET: polyester; SPF: sugar palm fibre [276].

flame-retardant properties. The study highlighted the importance of retardant performance of these hybrid composites.
fibre-matrix compatibility and interfacial bonding in achieving effective In a study by Asmawi Nazrin et al. [280], the flammability and
flame retardancy. Good bonding ensures that the fibres are well inte­ physical stability of sugar palm crystalline nanocellulose reinforced
grated into the matrix, enhancing the composite's mechanical properties thermoplastic sugar palm starch/poly (lactic acid) blend bio nano­
and its ability to form a protective char layer during combustion. composites were examined, as depicted in Fig. 6. The flammability test,
Additionally, the moisture content in SPF can enhance the flame retar­ conducted following ASTM D635 standards, involved pre-heating sam­
dant effect of Mg(OH)₂ by contributing additional water vapour during ples measuring 125 mm × 13 mm × 3 mm for 24 h at 100 ◦ C to remove
decomposition, which helps to cool the material and suppress flames. moisture. These samples were ignited at one end, and the time taken for
Overall, the findings underscore the critical role of both the composition the flame to travel a distance of 100 mm was recorded [280]. This
and the interaction between components in determining the flame- allowed for the calculation of the burning rate using Eq. 2: The burning

Fig. 6. Experimentation setup for the LOI test of PLA/TPS [280].

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M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

rate (V), expressed in millimetres per minute (mm/min), quantifies the PLA60TPS40, led to higher burning rates and lower resistance to com­
speed at which a material burns. It is calculated using the equation: bustion [280].
The study illuminate's lignin's role in char formation and flame
L
V= (2) propagation inhibition within cellulose, yet the removal of lignin to
t
produce SPCNC with lower water retention may have inadvertently
where L is the burnt length (the distance the flame travels along the increased the flammability rate in samples with higher TPS content.
sample in millimetres), and t is the time taken for the flame to travel that Additionally, the research underscores glycerol migration from TPS to
distance, measured in minutes. PLA during the melt mixing process, attributed to its lower molecular
The flammability of natural fibre composites is predominantly weight, which enhances the PLA phase's flammability [285]. This em­
influenced by the cellulose content of lignocellulosic fibres, which are phasizes the need for further investigation to strike a balance between
inherently combustible. Treatment methods such as alkaline and ben­ flammability and performance in PLA/TPS blends.
zoylation significantly affect the mechanical and thermal properties of The UL94 rating suggests that both PLA40TPS60 and PLA60TPS40
these materials. Alkaline treatment improves mechanical strength but exhibit a burning rate of less than 40 mm per minute, indicating high
increases flammability by exposing cellulose. Conversely, benzoylation flame retardancy. This has led researchers to further contemplate
introduces hydrophobic benzoyl groups that enhance char formation replacing glycerol with glycerol phosphate to enhance the flame-
during combustion, effectively reducing the burning rate. Incorporating retardant properties of starch-based polymer blends. In conclusion,
flame retardant additives like magnesium hydroxide (Mg(OH)₂ further this study comprehensively analyses the flammability characteristics of
enhances fire resistance through endothermic decomposition, which PLA/TPS blends, highlighting the necessity for additional research to
releases water and cools the material. Additionally, optimizing the fibre- improve their performance and safety [283–285]. Babu et al. [286]
to-matrix ratio is crucial to ensure effective interfacial bonding, thereby thoroughly investigated the thermal-flammability and mechanical per­
limiting flame spread and preserving the composite's structural integ­ formance of coir fibre-reinforced biocomposites. Raw coir fibres were
rity. By combining benzoylation treatment, Mg(OH)₂ additives, and treated with a 5 % sodium hydroxide solution at 50 ◦ C, and composites
optimized fibre-matrix interactions, the fire safety of natural fibre were fabricated using varying weight percentages of treated and raw
composites can be significantly improved. This integrated approach coir fibres (10 %, 20 %, and 30 % by weight).
enhances flame resistance and makes these materials more viable for The burning characteristics of the composites were evaluated using a
applications in lightweight construction where fire performance is Limiting Oxygen Indexer (Dynisco Instrument), with samples sized at 80
critical. mm × 10 mm × 4 mm [286]. The LOI measures the relative flamma­
The LOI test, conducted under ASTM D2863, was also employed to bility of polymeric materials, with polyolefins generally being more
determine the minimum oxygen concentration required for combustion. susceptible to flames. Real-world scenarios encompass various factors
In this experiment, samples measuring 100 mm × 6.5 mm × 3 mm were influencing material flammability, such as flame propagation, fuel
pre-heated for 24 h at 100 ◦ C to eliminate moisture and ignited for 10 s feeding, and charring [284,286,287]. The pure PE matrix exhibited
[281,282]. To calculate the LOI value, Eq. (3) was used: rapid burning, releasing polymer droplets and displaying an LOI value of
17 %. However, the addition of coir fibres altered the composites'
Cf = k + d (3) burning characteristics [286]. Fibres notably reduced polymer dripping,
Here, and Fig. 7 displays a linear correlation between fibre content in raw and
Cf = The final concentration of oxygen, alkali-treated fibre composites.
k = Constant derived from the Fire Testing Technology manual, and. Theoretically, the LOI can be calculated using the char residue ob­
d = Represents the increment in oxygen concentration. tained from the Thermogravimetric Analysis of the composites. Table 4
These variables are typically expressed as percentages (%). presents a comparison between the experimentally obtained LOI and the
Various blends comprising polylactic acid (PLA) and thermoplastic theoretically calculated LOI based on char residue [286]. In both cases,
starch were evaluated for their flammability properties [280]. The re­ the theoretical value was notably higher than the experimental value.
sults showed a slightly higher Limiting Oxygen Index (LOI), a critical This discrepancy can be attributed to the theoretical calculation relying
measure of flammability, for the PLA40TPS60 blend at 19.2 % compared solely on the residual char mass of the composites without accounting
to the PLA60TPS40 blend at 18.8 %. These findings align with Bocz for other factors influencing flammability.
et al.'s report, where TPS plasticised with 25 % glycerol and PLA/TPS
plasticised with 5 % glycerol demonstrated similar LOI values [280].
Interestingly, despite having the highest glycerol concentration, the
PLA20TPS80 blend exhibited the lowest flammability level among the
three blends. This suggests that a higher TPS content, indicating a higher
sugar palm crystalline nanocellulose (SPCNC) concentration, requires
increased oxygen concentration during combustion [283,284].
Flammability tests revealed distinct burning behaviours among
pristine PLA and PLA/TPS bio-nanocomposites. The PLA20TPS80 blend
was classified as inflammable, emitting moderate smoke, a low flame,
and undergoing partial burning. Similarly, PLA70TPS30, PLA80TPS20,
and pristine PLA (PLA100) showed inflammable characteristics, with
moderate smoke and low flames, demonstrating resistance to sustained
combustion. The PLA40TPS60 and PLA60TPS40 blends exhibited
measurable burning rates under horizontal tests. PLA40TPS60 burned at
16.39 mm/min with an LOI of 19.2 %, while PLA60TPS40 burned at
15.29 mm/min with an LOI of 18.8 %. Both blends burned completely
dripped rapidly, emitted minimal smoke, and maintained low flames.
These findings highlight the influence of TPS content on flammability.
Higher TPS content, as in PLA20TPS80, enhanced flame resistance,
while lower TPS concentrations, such as in PLA40TPS60 and
Fig. 7. LOI test on raw and alkali-treated fibre composites [286].

17
M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

The proposal to replace glycerol with phosphate presents an inno­ contributing to flame retardation. This mechanism retards the heating of
vative approach to further improving the flame-retardant properties, as materials in a fire by absorbing energy. Among the samples with natural
glycerol phosphate may enhance thermal stability and char formation. fibre, epoxy/PET/KF-50 displayed the highest average burning rate,
Similarly, Babu et al. [286] explored coir fibre-reinforced bio­ potentially influenced by environmental conditions that accelerate the
composites, revealing that sodium hydroxide treatment significantly burning process [279,288,289].
improved flame resistance, as shown by the Limiting Oxygen Index Notably, the transition of composite characteristics toward ligno­
(LOI). Incorporating coir fibres effectively reduced polymer dripping cellulosic materials at higher fibre contents fosters char formation,
and altered burning characteristics, underscoring the advantages of which can simultaneously provide thermal protection and increase
natural fibres in enhancing fire performance. Future research could smoke density. The melting of PET yarn within the epoxy/Mg/PET
focus on optimizing treatment conditions for coir fibres, exploring the composite further complicates combustion dynamics, highlighting the
synergistic effects of alternative flame retardants, and conducting fire need for careful consideration of polymer interactions during fire
tests under real-world scenarios to inform the development of safer, exposure. The endothermic reaction of magnesium compounds not only
more reliable biocomposite materials. aids in char formation but also contributes to flame retardation, indi­
Drawing from the research conducted by Suriani et al. [100], a cating a potential pathway for improving fire safety. This will be crucial
thorough investigation was carried out on epoxy composites reinforced for developing safer, environmentally friendly materials that meet the
with kenaf fibre and PET yarn. To assess the burning rate, a compre­ rigorous demands of modern construction.
hensive burning test was conducted following ASTM standard D635 Shewalul et al. [290] examined the fire response characteristics of
[286–288]. Each specimen, precisely cut to dimensions of 12.5 cm two distinct materials: hemp shives and hemp block samples. This
length, 1.3 cm width, and 0.3 cm thickness, underwent exposure to a analysis employed the robust methodology of cone calorimeter tests,
specified gas flame for 30 s in a horizontal orientation. The duration and adhering to stringent standards such as ASTM E1354 [291,292], ISO
extent of burning were meticulously recorded, and the material's 5660-1 [292], and NFPA 271 [293]. These tests have proven invaluable
average burning rate was calculated if it burned up to the 100 mm mark in evaluating the reaction-to-fire properties of these materials. The
from the ignited end, as illustrated in Fig. 8(a) [288]. experimental design involved two distinct configurations of test mate­
Analysing the horizontal burning test results illustrated in Fig. 8, the rials: hemp shives and hemp block samples. The dispersed nature of
average burning rate was calculated for each sample. The resin's exposed hemp shives necessitated a volumetric approach for their preparation.
surface volume fraction to the flame affects the ignition time due to the To ensure an accurate estimation of intrinsic factors, the samples un­
fibre content. In the case of epoxy/Mg/PET, the PET yarn melted and derwent oven-drying at a temperature of 105 ± 2 ◦ C for 24 h. This
moved away from the flame, leading to a smoky flame. Among the process effectively minimised the impact of moisture on the fire prop­
composites containing 35 % KF and 5 % magnesium hydroxide, those erties. Conversely, the hemp blocks were precisely cut to measure 100
with the same composition demonstrated superior performance, dis­ mm × 100 mm with a thickness of 50 mm [290].
playing the lowest average burn rate at 14.553 mm per minute, as shown Excluding the top surface, the specimens were enveloped in
in Fig. 8(b). This highlights the best fire retardant efficacy achieved with aluminium foil and positioned within a standard specimen holder.
the fibre volume content of epoxy/PET/KF-35 [288,289]. Subsequently, they were subjected to irradiances of 35 kW m − 2 and 50
When the fibre content surpasses 20 %, the composite's character­ kW m− 2. The study employed a typical pilot spark igniter, with data
istics start resembling lignocellulosic materials. Kenaf fibre tends to collection continuing for a minimum of 30 min after sustained flaming
foster char formation and heightens smoke density when subjected to or if the specimen remained unignited for 30 min [290]. This research
flames. In the case of flame exposure to epoxy/PET/KF-35, char for­ underscores the significance of comprehending the combustion behav­
mation occurs simultaneously [288]. Char results from the chemical iour of these materials and their potential fire hazards, offering insights
reaction between magnesium and the flame, causing incomplete com­ for safer and more sustainable construction practices. Further explora­
bustion of certain solids at high temperatures, eliminating hydrogen and tion is essential to delve deeper into these findings and expand our
oxygen from the char, leaving behind carbon. The endothermic knowledge in this critical area of study. Such efforts will undoubtedly
decomposition of the magnesium compound releases hydration water, contribute to the development of safer, more sustainable construction

Fig. 8. Horizontal burning test results for each composition. (a) Physical changes during the burning test. (b) Burning rates for each composition. PET: polyester; KF:
Kenaf fibre [288].

18
M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

materials. The study conducts a detailed analysis of hemp shives and higher irradiances, suggesting susceptibility to ignition in the presence
blocks using cone calorimeter testing. It aims to comprehend their of open flames or high temperatures. Its CHF was notably lower (5 ± 0.5
combustion behaviour, potential fire hazards, and the impact of varia­ kW m− 2) than that of other construction materials like wood, often
tions in irradiance, while also exploring the differences in fire behaviour around 12 ± 2 kW m− 2, owing to its fibrous geometry. Hemp shiv's
between the shives and blocks. ignition temperature, calculated at 206 ◦ C, slightly below the typical
Visual observations offer insights into the behaviour of hemp shivs range for wood and similar materials (220 to 250 ◦ C), indicates a higher
during the cone calorimeter test. Captures the pre-ignition stage, char­ vulnerability to ignition, possibly due to its geometry and pyrolysis rate.
acterized by the production of pyrolysis gases. There was no noticeable Conversely, hemp blocks exhibited remarkable fire resistance, remain­
mass loss at this stage, and the HRR remained minimal. The ignition ing unignited during the test period. The blocks showed lower HRR
stage, where the HRR gradually increased, reaching the pHRR. This peak compared to the shiv, credited to the lime binder's ability to absorb
is observed during the third stage, the sustained flaming period, during energy, reduce heat transfer to the shiv, and curtail the production of
which the sample continued to burn with a low flame intensity for the pyrolysis gases [290]. Table 5 presents a comprehensive analysis of the
remaining test duration. This combustion behaviour remained consis­ fire behaviour of hemp shiv and blocks, emphasizing critical parameters
tent at irradiance levels of 35 and 50 kW m− 2 [290]. Fig. 9(a) presents like TTI, CHF, HRR, THR, MLR, and FIGRA.
the results of the cone calorimeter test, highlighting the distinctive The analysis revealed distinct differences in the evaluation of the fire
combustion behaviour between hemp shives (Fig. 9a) and hemp blocks behaviour of hemp shiv and hemp blocks under various irradiance
(Fig. 9b). When heat exposure, the hemp shives burned utterly, leaving levels. Hemp shiv consistently reached pHRR faster than hemp blocks
minimal residual matter. In contrast, the hemp blocks exhibited a slow across different irradiance levels. The Effective Heat of Combustion was
charring effect, with a measured char depth of only 15 mm after 30 min. notably higher for hemp shiv due to lime's minimal calorific value, with
This improved behaviour is attributed to the lime binder within the slight variations related to sample conditions and heat transfer. Both
blocks, resulting in a non-combustible matrix encapsulating the shiv materials exhibited a sharp increase in the Maximum Heat Release Rate,
particles [290]. peaking before declining due to reactant exhaustion. Hemp blocks
An intriguing observation was the remarkably low smoke production showed a higher MLR, potentially due to moisture content. Although the
from the hemp blocks [290]. Given the limited smoke generation and THR was significant for hemp shiv at higher irradiance, the presence of a
the sample's nature, it suggests the emissions from hemp blocks are lime binder in hemp blocks mitigated this, reducing their potential fire
likely non-toxic [294]. However, additional research is required to hazard. Both materials demonstrated a relatively low FIGRA, with hemp
characterize the smoke emissions precisely. This study emphasizes the blocks recording a lower FIGRA than hemp shiv [290].
significance of comprehending the combustion behaviour of these ma­ Another critical test in this comprehensive analysis involved
terials and their potential fire hazards, advancing the path toward safer comparing bomb calorimeter and cone calorimeter tests, as presented in
and more sustainable construction practices. Further investigation is Table 6. The gross heat of combustion for hemp shiv was determined as
essential to delve deeper into these findings, enriching our under­ 23.2 MJ kg− 1, comparable to reported values for hemp pellets used as
standing in this critical field of study. Such efforts undoubtedly biomass fuel (18.5 MJ kg− 1). In contrast, hemp blocks exhibited a lower
contribute to developing safer, more sustainable materials for the con­ calorific value at 7.4 MJ kg− 1. This divergence can be attributed to hemp
struction industry. shiv's higher cellulose and lignin content, which possess higher calorific
This study presents a comprehensive analysis of the fire behaviour of values, and the lime-based binder in hemp blocks, contributing negli­
hemp shiv and blocks, focusing on critical parameters such as TTI [295], gible energy. Notably, the bomb calorimeter test yielded higher heat of
Critical Heat Flux (CHF) [296], HRR [297], THR [298], MLR [299], and combustion values for both samples compared to the cone calorimeter
fire growth rate (FIGRA) [300]. The study unveils significant insights test, likely influenced by moisture content, as the cone measures net
into the fire behaviour of hemp shiv and hemp blocks. Hemp shiv combustion heat. This comprehensive review highlights the imperative
demonstrated high combustibility, displaying a reduced TTI under of comprehending construction material fire behaviour to ensure

Fig. 9. Images of (a) Residual Hemp Shiv and (b) Charred Hemp Blocks with a Charring Depth of 15 mm [290].

19
M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

Table 5
Fire behaviour of hemp shiv and blocks, with a focus on TTI, CHF, HRR, THR, MLR, and FIGRA [290].
Sample block Fire properties TTI (s) pHRR TpHRR EHC MLR10–90 THR (MJm− 2) FIGRA (kWm− 2 − 1
s ) CHF
2 1
(kW m− ) (s) (MJ kg− ) (gm− 2 s− 1)b (kW m− 2
)
− 2
Hemp shiv 35 kW m 11.2 189.3 55 11.7 3.4 71.6 4.1 5 ± 0.5
2
50 kW m− 8. 225.1 55 14.9 3.6 98.5 3.4
4
2
Hemp block 35 kW m− a 22.9 135 5.7 1.9 21.6 0.17 a
2
50 kW m− A 22.3 135 5.9 2.2 22.1 0.17 a

(a) Hemp blocks showed high ignition resistance (did not ignite)
(b) MLR10–90 represents the average mass loss rate per unit area between 10 % and 90 %.

7. NFRPCs in flammability and fire resistance applications

Table 6
Analysing the differences in combustion heat results from bomb and cone cal­
Natural fibres are increasingly influential across various sectors,
orimeters [290].
driven by the imperative need for sustainability rather than mere
Sample Sample Average trendiness. They offer several advantages over synthetic counterparts,
1 2 3 including cost-effectiveness, lightweight characteristics, reduced wear
Gross heat of combustion (MJ kg − Hemp 23.1 22.9 23.6 23.2 on processing equipment, and improved surface finish in composite
1
) for bomb calorimeter results shiv molded parts. These attributes make them highly attractive in diverse
Hemp 7.8 7.2 7.3 7.4 sectors like aerospace, automotive, furniture, packaging, and construc­
block
tion [301,302]. Additionally, natural fibres boast superior mechanical
Effective heat of combustion (MJ Hemp 14.0 14.8 15.8 14.9
kg− 1)for cone calorimeter at 50 shiv
properties relative to their weight, are renewable, and abundant, possess
kW m− 2 Hemp 6.1 4.3 7.4 5.9 a high aspect ratio, and exhibit flame-retardant properties [270,303].
block Their versatility is evident in numerous applications, from building
materials, particle boards, and insulation boards [304–306], to serve as
raw materials for cosmetics, medicine, other biopolymers, and fine
building industry safety and sustainability [290].
chemicals [307,308]. Fire-resistant polymers are indispensable for
The research conducted by Shewalul et al. [290] thoroughly exam­
construction in scenarios where escape routes are restricted, such as
ines hemp shives and blocks, delving into their combustion behaviour
skyscrapers, boats, and aeroplane cabins [309]. The critical role of fire
and potential fire hazards. It underscores the significance of compre­
resistance becomes evident from studies revealing that fatalities in
hending these elements to foster safer and more sustainable construction
aeroplane crashes are often due to post-crash fires rather than the impact
practices. Furthermore, the study accentuates the importance of further
itself [310,311]. These polymers are also pivotal in aerospace adhesives,
exploration to improve the fire resistance of hemp shiv and enhance the
electronics insulation, and military materials like canvas tents [312],
performance of hemp blocks. Such efforts play a pivotal role in
emphasizing their crucial role in safeguarding lives and property.
advancing the creation of safer, more environmentally friendly building
Additionally, their utility extends to tissue engineering and agricultural
materials.
applications due to their inherent biodegradability, sustainability, and
A notable finding was the observed reduction in pHRR in conjunction
superior biocompatibility, making them integral in reducing environ­
with a relatively stable THR. This dichotomy highlights the intricate
mental impact while promoting advancements in the medical and
combustion behaviours inherent to natural fibres like hemp. These
agricultural sectors [313,314].
materials decompose at relatively low temperatures, facilitating the
Advancements in the field of intelligent fire detection materials and
early release of volatiles that contribute to a diminished heat of com­
sensors are being pursued. This involves the integration of conventional
bustion. This phenomenon leads to a lower pHRR as the combustion
flame retardant methodologies with proactive fire alarm response
process progresses. Moreover, the char-forming behaviour exhibited by
mechanisms. This approach aims to enhance fire safety measures by not
natural fibres complicates the combustion dynamics; as they undergo
only preventing the spread of fire but also providing timely alerts in the
combustion, they generate an insulating char layer that acts as a thermal
event of a fire outbreak. This is a significant stride toward improving fire
barrier, effectively moderating heat release during subsequent com­
safety protocols and reducing potential fire-related hazards [315]. This
bustion phases. This behaviour is particularly significant when
study can significantly enhance fire detection systems. Understanding
comparing bio-based materials to synthetic counterparts, often exhib­
material flammability and fire resistance can improve the precision of
iting markedly different combustion characteristics.
fire alarms. Sensors can be calibrated to detect specific smoke or heat
Integrating natural fibres such as hemp into polyolefins offers sig­
from burning natural fibres. Predicting the materials that ignite first aids
nificant potential, particularly when combined with flame retardants
in strategic detector placement. Improved fire behaviour predictions can
like ammonium polyphosphate (APP). APP releases gases such as
lead to quicker, more accurate alarm responses, reducing risks and
ammonia and water vapour during decomposition, diluting the com­
potentially revolutionizing fire safety measures.
bustion atmosphere, reducing the HRR, and maintaining a stable THR
The automotive industry increasingly adopts natural fibres for
through smouldering combustion. Similarly, lime binders in hemp
manufacturing interior components like door panels, seat covers, and
blocks act as thermal stabilizers, sequestering heat and slowing charring.
dashboard parts [316]. Besides reducing vehicle weight, their use en­
These mechanisms emphasize the importance of understanding emis­
hances the interior's aesthetics, improving fuel efficiency [317]. More­
sions profiles and char formation to optimize fire safety in bio-based
over, components made from natural fibres do not emit toxic fumes
materials. The study also highlights practical considerations for appli­
during fires, unlike their synthetic counterparts. The furniture industry
cations. The low smoke production from hemp blocks suggests advan­
embraces natural fibres due to their aesthetics, outstanding insulation
tages for indoor air quality, while the higher calorific value of hemp shiv
properties (particularly suitable for outdoor furniture), durability, and
indicates increased combustibility. Continued research is crucial to
eco-friendly nature [67,318]. For the packaging sector, the utilization of
enhance the fire performance of hemp-based construction materials,
natural fibres leads to the production of biodegradable packaging ma­
promoting their viability as sustainable, fire-safe alternatives in the
terials that decompose naturally, reducing landfill waste [319].
building industry.
Furthermore, these materials have excellent thermal and mechanical

20
M.H. Mulla et al. International Journal of Biological Macromolecules 305 (2025) 141130

properties, catering to various packaging applications [319–321]. In assessments, can provide a deeper understanding of NFRPCs' combus­
construction, natural fibres are employed in eco-friendly building ma­ tion properties, enhancing fire performance evaluations and supporting
terials renowned for their excellent insulation and resistance to pests the development of more effective fire-retardant materials.
and mold, thereby enhancing structural durability [304,322–324].
However, the variability in natural fibre properties poses a challenge 9. Conclusion
affecting the final product's performance [325,326]. To tackle this
challenge, ongoing research is dedicated to standardizing the properties This comprehensive review synthesizes diverse studies on NFRPCs,
of natural fibres. Despite the challenges, the multifaceted advantages of highlighting their potential as environmentally friendly materials with
natural fibres underscore their significance across diverse industries. robust mechanical strength. However, challenges persist due to their
Ongoing research and technological advancements are set to further susceptibility to immediate ignition and rapid burning, attributed to the
enhance their applications. Natural fibres are poised to be pivotal in hydrocarbon-based polymers and cellulose in plant fibres. The thermal
promoting a sustainable future due to their contributions to sustain­ decomposition of these polymers, typically occurring between 300 and
ability and reduced environmental impact. NFRPCs find applications in 500 ◦ C, generates hazardous by-products, necessitating a nuanced un­
various sectors. Notably, they are utilised in marine construction, such derstanding of their flammability to ensure safety across industries. The
as the TaraTari boat crafted from jute fibres and the Flax 27 sailing boat fire performance of NFRPCs, influenced by factors such as fibre volume
constructed with flax laminate. Additionally, hybrid boats made from content, matrix type, surface treatments, and filler concentrations, is
sugar palm and glass fibres showcase the versatility of NFRPCs. evaluated through various test techniques, with ASTM D635 serving as a
In the automotive industry, construction, and interior design, crucial benchmark. Hybridizing natural fibres with other materials and
NFRPCs are making significant inroads. They are used in car compo­ applying flame-retardant coatings significantly enhance NFRPCs' per­
nents, insulation boards, bamboo roofs, and wood grain wall panels, formance against fire under diverse conditions.
highlighting their diverse applications. Furthermore, NFRPCs are The NFRPCs' flammability and fire resistance field represent an
employed in aircraft components, including carriage doors and seat emerging area for future exploration. Investigating NFRPCs' inherent
panelling, with potential applications in radomes underscoring their flammability characteristics, their response to high temperatures, and
versatility. NFRPCs must exhibit high thermal and fire resistance to the factors influencing their thermal behaviour offer intriguing avenues
ensure safety and durability. Their potential to advance a sustainable for further study. Enhancing fire resistance in these composites could be
future remains a compelling aspect of their use. achieved through advancements in surface treatment methods and
optimizing filler concentrations. Developing novel flame retardant
8. Challenges and future scope compounds for coating, hybridizing, or encapsulating natural fibres
could significantly bolster NFRPCs' fire resistance. Adopting varied test
Fire retardants embedded in NFRPC face significant challenges. One techniques, from bench-scale to full-scale assessments, could yield a
major issue is the high production cost. Incorporating flame retardant deeper understanding of these materials' combustion properties.
additives, modifying fibre surfaces, or using fire retardant polymers can Exploring NFRPCs' applications in industries with stringent safety
be expensive, impacting cost-effectiveness for various applications. requirements, such as automotive, aerospace, furniture, and construc­
Additionally, these modifications can negatively affect the composites' tion, could lead to the development of safer, more sustainable products.
mechanical properties, such as toughness and stiffness, making it chal­ This future scope aligns with the global shift toward environmentally
lenging to balance fire resistance with mechanical performance. friendly practices, highlighting NFRPCs' pivotal role in advancing
Another challenge is the lack of standardized testing methods for environmental sustainability. This promising trajectory emphasizes the
assessing NFRPC's fire resistance, complicating product comparisons significance of NFRPCs in shaping a sustainable future.
and evaluations. The availability of certain plant fibres, like banana,
sisal, and jute, is limited in some regions, hindering large-scale pro­ CRediT authorship contribution statement
duction of fire-retardant NFRPC. Ensuring uniform dispersion of flame
retardants within the fibre matrix is also difficult; uneven distribution Mohammed Huzaifa Mulla: Writing – review & editing, Writing –
can lead to inconsistent flame resistance. Furthermore, the long-term original draft. Mohd Nurazzi Norizan: Writing – review & editing,
durability and performance of NFRPCs under varying environmental Writing – original draft. Nurul Fazita Mohammad Rawi: Validation,
conditions pose a challenge, requiring sustained fire-retardant effi­ Supervision. Mohamad Haafiz Mohamad Kassim: Validation, Super­
ciency. Developing flame-retardant NFRPCs without compromising vision. Che Ku Abdullah: Visualization, Validation. Norli Abdullah:
sustainability remains a significant hurdle, as eco-friendly solutions Visualization, Validation. Mohd Nor Faiz Norrrahim: Validation, Su­
must balance fire resistance with environmental impact. pervision, Conceptualization.
The field of fire-retardant NFRPCs offers numerous research and
development opportunities. Developing new, eco-friendly flame re­ Declaration of competing interest
tardants specifically for NFRPCs is a prominent avenue. Advances in
manufacturing techniques, such as surface modification of fibres and The author declares no conflict of interest, and it's an original work.
nanotechnology applications, can improve fibre polymer interactions
and enhance fire resistance. The growing stringency of fire safety reg­
Acknowledgements
ulations and market demand for sustainable materials highlight the
potential for fire-retardant NFRPCs in various industries, including
Special thanks to Universiti Sains Malaysia for the financial assis­
automotive, aerospace, construction, and marine sectors.
tance through the Second Short Term Grant (304/PTEKIND/6315733).
Collaborative efforts among material scientists, chemists, engineers,
and manufacturers are expected to yield breakthroughs in designing
Data availability
fire-safe natural fibre composites. Interdisciplinary research can inte­
grate enhanced performance with sustainability, driving the evolution
No data was used for the research described in the article.
and application of these materials. As technology advances and pro­
duction processes become more efficient, the cost of producing fire-
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