Review Article

Journal of Fire Sciences

Flame retardancy of 1–36
Ó The Author(s) 2025
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DOI: 10.1177/07349041241309308
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retardants: A review

Thobile L Mhlabeni1,2 , Endazenaw B Chemere1,

Tamba Jamiru2 and Washington Mhike1
Date received: 30 August 2024; accepted: 9 December 2024

Abstract
The demand for sustainable materials has led to the development of biopolymers as alternatives
to petroleum-based polymers. However, their high flammability limits their use in applications
requiring stringent fire safety. Bio-based additives such as lignin and chitosan among others have
charring abilities that enhance flame retardancy by forming protective barriers during combustion.
Renewable additives such as phytic acid, tannic acid, casein, and hydrophobins also show potential
in improving polymer dehydration, which can help create a stable char layer. Phosphorylation and
the use of nitrogen-containing compounds and nanomaterials show promise in improving
fire resistance. These advancements make biopolymers more suitable for high-risk fire safety
applications while maintaining sustainability. While considerable progress has been made in
enhancing the flame retardancy of biopolymers, challenges remain in developing highly
effective, non-toxic, and fully biodegradable flame retardants that do not compromise the physical
properties and processability of the biopolymers.

Keywords
Biobased, flame retardant, biopolymers, flammability

1
Polymer Technology Division, Department of Chemical, Metallurgical and Material Engineering, Tshwane University of
Technology, Pretoria, South Africa
2
Department of Mechanical and Mechatronics Engineering, Tshwane University of Technology, Pretoria, South Africa

Corresponding author:
Thobile L Mhlabeni, Polymer Technology Division, Department of Chemical, Metallurgical and Material Engineering,
Tshwane University of Technology, Pretoria 0183, South Africa.
Email: [email protected]
2 Journal of Fire Sciences 00(0)

Introduction
Biopolymers, derived from renewable resources, have garnered significant attention due to
their sustainability, biodegradability, and biocompatibility. Biopolymers offer a promising
alternative to conventional polymers, in applications requiring these properties. However,
polymers in general naturally exhibit low temperature endurance and stability. Polymers are
prone to ignition and rapid flame spread due to their organic nature. In general, the flamm-
ability of polymers is influenced by factors such as thermal stability, degradation pathways,
and the presence of flammable volatile compounds.1,2 Consequently, polymers in general
pose a fire hazard in various settings, including households, hospitals, schools, and industrial
settings. To mitigate this hazard, flame retardants have been extensively applied as an effec-
tive strategy to delay or prevent polymer disintegration and decomposition.3,4 Enhancing the
flame retardancy of biopolymers is crucial for expanding their applications in fields requiring
stringent fire safety standards. The aim of this work is to review strategies for flame-retarding
biopolymers using environmentally friendly flame retardants/bio-based flame retardants.
Flame retardancy is a concept that involves a material’s ability to reduce flammability
and slows the spread of fire.5 Flame retardants are commonly used to depress flame propa-
gation chemically and physically in the solid, liquid, or gas phase.6–8 An effective flame
retardant must possess several key characteristics to ensure good flame retardancy. The key
characteristics of effective flame retardants include heat absorption.9 Heat absorption can
occur through endothermic decomposition, where the material absorbs heat as it breaks
down. This heat absorption helps to lower the temperature of the material, delaying ignition
and slowing the spread of fire. In addition, some flame-retardant release inert products such
as water vapor, carbon dioxide, or other non-flammable gases. These gases help to cool the
material and dilute the concentration of flammable gases, thus inhibiting combustion.
Another possible characteristic is free radical scavenging.10 Some flame retardants can
release reactive products that function as free radical scavengers. These products quench the
chemical reactions that occur during combustion by neutralizing free radicals, thereby slow-
ing down or stopping the combustion process. Another possible characteristic of flame retar-
dants is char formation. The char creates an insulating layer on the surface of the burning
material.11 The formed char then limits the diffusion of oxygen to the material and decrease
the release of combustible gases by trapping volatile degradation products.12
The common flame retardants used are based on halogenated compounds.13,14
Halogenated flame retardants are known for their high effectiveness, particularly those con-
taining chlorine and bromine, but they also come with significant drawbacks. Halogen-con-
taining flame retardants pose significant challenges due to their persistence,
bioaccumulation, high toxicity, and adverse environmental impact.13,15 Due to these draw-
backs, halogenated flame retardants have come under increased regulatory scrutiny. Their
use is currently under restriction or phased out.15–19 Numerous other flame-retardant mate-
rials, including transition metal (zinc, magnesium, aluminum, antimony, tin) oxides or
hydroxides, have been extensively explored for their effective flame retardancy for poly-
mers.16–19 Phosphorus-based, carbon-based, nitrogen-based epoxy resins, nano-inorganic
particles, and so on, flame retardants also offer good fire retardancy, making them a viable
alternative to halogen-based flame retardants.20 In addition, organo-phosphorus flame
retardants are also widely applied due to their effectiveness and function through both gas-
phase and condensed-phase mechanisms.21 Insulating char-forming or intumescent flame
retardants are also a promising eco-friendly alternative to halogen flame retardants. An
Mhlabeni et al. 3

intumescent flame-retardant system consists of an acid source, a blowing agent, and a char
former. Intumescent technology has long been applied as an advanced system offering flame
retardancy to polymeric materials.3 A typical intumescent system for polyolefin-based poly-
mers has been explored.3,22 The system comprised of ethylene-butyl acrylate-maleic anhy-
dride as the base polymer, ammonium polyphosphate (APP) as both an acid source and a
blowing agent, and pentaerythritol (PER) as the carbon source.3 Since then, this technology
has attracted substantial interest due to its versatility, effectiveness, and relatively lower
environmental impact than traditional flame retardants.1
A broad spectrum of the aforementioned fire retardants has highlighted their importance
in fire safety. Their effectiveness strongly depends on their composition and the mechanisms
by which they retard flames.22,23 The development and use of these materials involve apply-
ing them effectively by conducting rigorous testing to ensure performance.24,25 However, the
release of toxic gases during combustion and decomposition, although in relatively small
amounts to halogen-containing flame retardants, still pose a significant human and environ-
mental health risks.13,14,18 Consequently, there is growing interest and demand for flame
retardants with reduced or no toxicity and environmental impact. While bio-based materials
are increasingly explored for these purposes, it is important to note that bio-based polymers
or additives are not inherently non-toxic. The development of relatively safer, low-toxicity
flame retardants, including bio-based options, is a key focus to meet the growing consump-
tion of plastics and natural materials.23,26–29 This trend aims to reduce environmental
impacts. Advances in sustainable and eco-friendly flame retardants are shaping the future of
this field, promoting the development of more safer and sustainable products.30
Bio-based materials such as lignin, chitosan (CS), phytic acid (PA), proteins, and starch
among others are rich in functional groups that include aromatic rings, hydroxyl, phos-
phorus, and nitrogen groups. These functional groups contribute to intumescent flame retar-
dancy by promoting and contributing to char formation during combustion. Combining
bio-based materials with other flame-retardant components, such as APP, organically modi-
fied montmorillonite (OMMT), and halloysite nanotubes (HNTs), often results in synergis-
tic effects, enhancing overall flame retardancy.31–33 Recent studies have also focused on
optimizing the dispersion and interaction of bio-based flame retardants within polymer
matrices to maximize their efficiency.34–36 Techniques such as layer-by-layer (LbL) assembly
and in situ polymerization have been employed to create nano-structured and well-dispersed
flame-retardant systems.30 This review provides a comprehensive overview of diverse types
of greener flame-retardant additives, their mechanisms, advantages and disadvantages,
methods for developing flame-retardant systems, and recent advancements in bio-based
flame-retardant additives for biopolymers.

Brief discussion on traditional flame-retardant systems

Preparation methods
Conventional methods for developing flame-retardant polymers involves using additive
flame retardants, which are melt-mixed with polymers.37–41 Another approach includes
incorporating reactive flame retardants directly into the polymer matrix through chemical
bonds.42 Surface flame retardants are applied as coatings on the polymer product’s surface
to enhance fire resistance.43–48 Each of these methods offers distinct advantages and selected
based on the specific requirements of the application, the type of polymer, and the desired
4 Journal of Fire Sciences 00(0)

level of flame resistance. For instance, inorganic flame retardants, such as aluminum hydro-
xide (ATH), magnesium hydroxide (MH), zinc borate, APP, nano-clays, and nano-silica,
are frequently applied as additive flame retardants though melt-blending.49–54 Organic flame
retardants including halogenated compounds, phosphorus-based compounds, epoxy resins,
and nitrogen-based compounds can be applied as additive or reactive flame retardants
through melt-blending or by in situ polymerization/grafting, respectively.55–58 On the other
hand, some flame retardants, such as phosphorus-based flame retardants, can be applied as
reactive oligomers, additives, and surface coatings. Similarly, intumescent flame retardants,
while often used as additive systems blended into the polymer matrix, can also be chemically
integrated into the material or applied as surface treatments.44,45,59,60 These flame retardants
provide an effective solution for improving the reaction-to-fire behavior of various materials
while offering a potentially less-toxic alternative to halogenated compounds.

Flame-retarding mechanisms
Halogen-based flame retardants function in the gas phase by interfering with the free radical
chain reactions involved in combustion.6 Tetrabromobisphenol A, hexabromocyclodode-
cane, and polybromodiphenyl ether compounds are commonly used halogenated flame retar-
dants.61,62 In combustion, such halogenated flame retardants release specific radicals, such as
chlorine (Cl) and bromine (Br), in the gas phase. The halogen radicals react with the highly
reactive combustible H and OH radicals to form less-reactive or even inert molecules.27,63
Red phosphorus and APP are a classic source of phosphorus for flame retardancy.64
Phosphorus (P)-based flame retardants primarily act in the solid phase of polymers by con-
tributing to the formation of a protective char layer and are also effective radical scavengers
in gas phases.65,66 They are particularly effective in the condensed phase, especially when
applied to oxygen-containing polymers.6,67 Herein, when exposed to intense heat, com-
pounds like phosphoric acid act as catalysts for polymer dehydration and cross-linking.5 In
the gas phase, phosphorus-containing flame retardants terminate the fire by releasing
phosphorous-containing radicals, such as PO2, PO, and HPO, to neutralize highly reac-
tive combustible species.5 In so doing, the released P- radicals disrupt the flame chemistry,
leading to flame inhibition. Phosphorus-based flame retardants are available in various oxi-
dation states, including phosphines (-3), phosphine oxides (-1), elemental phosphorus (0),
and phosphates ( + 5), among others.68 Typically, higher oxidation states of phosphorus, like
phosphates, tend to act primarily in the condensed phase, promoting char formation.69,70 In
contrast, lower oxidation states, such as those found in phosphines, phosphine oxides, or
phosphinates, are more likely to exhibit dual action, enhancing both gas-phase flame inhibi-
tion and condensed-phase effects.71,72 Moreover, phosphorus-based flame retardants are
known for their enhanced efficiency when combined with other types of flame retardants,
particularly nitrogen-containing flame retardants.72 This synergistic use enhances both gas-
phase and solid-phase flame-retardant mechanisms. For instance, nitrogen compounds fur-
ther enhance the dehydration process by catalyzing the polymer phosphorylation step.73 In
addition, nitrogen synergists help produce nonvolatile phosphorus acids as by-products,
contributing to the overall flame-retardant effect.74 Phosphorus-based flame retardants
are known for their high effectiveness and lower generation of toxic gases and smoke than
halogenated alternatives. But phosphorus-based flame retardants come in various forms,
including liquids and solids, and for this reason, some phosphorus compounds including red
Mhlabeni et al. 5

phosphorus and APP might interact with moisture and produce undesirable volatiles during
processing.75
Some flame retardants function by cooling or diluting the fuel or by forming a char layer
to inhibit combustion.76 Endothermic flame retardants produce a cooling effect by decom-
posing endothermically, absorbing heat, and releasing H2O, CO2, or other non-combustible
gases.63,77 Metal-based flame retardants such as metal hydroxides (e.g. aluminum tri-hydro-
xide, magnesium di-hydroxide), hydromagnesite, and zinc borates decompose endothermi-
cally.78 Absorption of heat lowers the temperature of the material, making it less likely to
ignite or sustain combustion. Metal-based flame retardants are highly effective due to their
inherently high temperature resistance and emission of non-toxic gases at elevated tempera-
tures. The challenge with metal-based flame retardants is the large amount of loading
required to be effective. This can lead to a significant reduction in the material’s mechanical
strength, flexibility, and overall processability.66,75,79
The incorporation of nanomaterials offers significant advantages as flame retardant.80
Nanoparticles, like carbon nanotubes, carbon black, montmorillonite (MMT), silica, and
graphene, have been reported to increase the material’s capacity to absorb and store heat
(thermal mass), thus promoting the formation of a protective char layer on the surface dur-
ing combustion.33,76,81–84 Herein, as the thermal mass increases, the polymer melt becomes
more viscous and less prone to dripping, which also contributes to stable char forma-
tion.85,86 Noteworthy, it is common that melt-dripping from pyrolyzing polymer may dissi-
pate heat and act as a new source of fire. However, in the former case, these nanoparticles
may delay volatile gases from fueling the combustion.87 The tortuous pathway established
by intercalation or exfoliation can act as physical barrier for volatile gases.88 Eventually, the
rising temperature facilitates the migration of the nanolayers to the surface where it forms a
stable char residue.82,89 On another note, the thermal decomposition of the organomodifier,
if present, creates strongly protonic catalytic sites on the inorganic filler surface.90 These
sites can catalyze the formation of a stable char residue. The char produced functions as a
poor heat conductor, creating a layer of insulation that retards heat transfer.76 By inhibiting
oxygen and hydrogen from the combustion process, the char layer helps to suppress further
combustion.67,91
Intumescent flame retardants, when exposed to fires, undergo chemical reactions resulting
in the material foaming, expanding, and charring.3 Intumescent flame-retardant systems
typically consist of an acid source, a carbon source, and a blowing agent. The acid source in
intumescent systems is typically a polyacid, such as APP or other phosphates. When exposed
to elevated temperatures, the acid source decomposes to release inorganic acids. The released
acid acts as a dehydrating agent. It removes water from the carbon source, leading to the for-
mation of a charred structure. The carbon source is essential for forming the foamed char.
The blowing agent decomposes to release gases such as ammonia (NH3), steam, and other
volatiles. These gases cause the char to expand and form a honeycomb-like structure, enhan-
cing its insulating properties.

Biopolymers and their flammability

Biopolymers have attracted significant attention due to their biological origin and properties
such as biodegradability and biocompatibility.92 However, their inherent flammability is a
significant limitation, especially in applications where fire safety is a concern. In most cases,
6 Journal of Fire Sciences 00(0)

biopolymers such polylactic acid (PLA), polybutylene succinate (PBS), poly(3-hydroxybuty-

rate) (PHB), and so on can ignite at temperatures above 270°C, making them susceptible to
catching fire during processing or in high-temperature environments. In the UL-94 vertical
flame test, biopolymers typically achieve a V-2 rating, demonstrating that they burn with
dripping.93,94 This rating indicates that while a material stops burning within a specified time,
it still poses a fire risk due to dripping flaming particles. The tendency of polymers to drip
when burning can be both advantageous and disadvantageous, depending on the application.
The advantages of dripping include the self-extinguishing behavior, for instance, removal of
fuel source and reducing heat transfer. In some cases, the dripping of molten polymer can
leave behind a charred residue that helps protect the underlying material from further degra-
dation. However, the disadvantage of dripping poses safety risks in various applications. A
disadvantage of dripping includes the creation of secondary fires. In addition, the loss of
material due to dripping can compromise the structural integrity of the polymer, leading to
failure in applications where mechanical strength is critical. Therefore, enhancing the flame
retardancy of these biopolymers is crucial for expanding their application in fields requiring
stringent fire safety standards. To address these challenges, various strategies have been
employed to enhance their flame retardancy.95–97
The pursuit of bio-based flame retardants for enhancing the flame retardancy of biopoly-
mers is presently an active area of research. This reflects the growing interest in sustainable
and environmentally friendly materials. Bio-based additives and fillers such as lignin, CS,
PA, casein, and cellulose are showing promising results in improving the flame retardancy of
biopolymers.98–100 The development of these materials holds significant potential for appli-
cations in the packaging, textiles, automotive, and construction industries, where flame-
retardant properties are crucial. Furthermore, by combining multiple bio-based additives,
researchers aim to develop high-performance biopolymer composites.

Bio-based flame retardants for PLA

PLA is a biodegradable and bioactive thermoplastic polyester derived from renewable
resources, such as corn starch or sugarcane.101 PLA is a polyester composed of lactic acid
monomers. The polymer can exist in two stereoisomeric forms: poly(L-lactide) (PLLA) and
poly(D-lactide) (PDLA). PLA can be processed using conventional plastic-processing tech-
niques, such as injection molding, extrusion, thermoforming, and 3D printing.102 It is one of
the most popular bioplastics used today due to its favorable mechanical properties, biode-
gradability, and versatility. PLA has attracted significant attention due to its biological ori-
gin and properties such as biodegradability and biocompatibility. However, its inherent
flammability is a significant limitation, especially in applications where fire safety is a con-
cern.98 By incorporating flame retardants, using natural fillers, and employing advanced
polymer design techniques, PLA can be tailored to meet the fire safety requirements of
various industries. Table 1 summarizes the flame-retardant systems that have been applied
to PLA. The table provides quantitative data on the flame performance metrics to illustrate
the enhanced effectiveness. The data include key parameters such as time to ignition (TTI),
UL-94 rating, limiting oxygen index (LOI), peak heat-release rate (pHRR), and char yield.

Cellulose. Cellulose is the most abundant organic polymer on Earth, found primarily in the
cell walls of plants.114 It is a key structural component of many natural fibers, including
Table 1. Bio-based flame-retardant systems applied on PLA and their effectiveness

Biopolymer Flame retardant Method of FR loading TTI UL-94 LOI pHRR Char Ref.
matrix application (Wt.%) (s) (%) (%) residue (%)
Mhlabeni et al.

PLA Cellulose nanocrystals Solution based 1.5 / V-2 / / / Bajwa et al.103

Cellulose (coating)-Bulk 1.5/1.5 / V-2 / / /
nanocrystals/zinc (melt-blending)
oxide
/ Cellulose / / / / / / 5.27 Dahiya and Rana104
Cellulose / / / / / / 26.6
phenylphosphonate
Cellulose 2- / / / / / / 33.4
dhlorophenyl-
phosphonate
Cellulose 2- / / / / / / 29.5
cresylphosphonate
PLA / Solution based / 86 / / / 0 Costes et al.105
Microcrystalline (coating)-Bulk 20 71 / / 7.70 0
cellulose (MCC) (melt-blending)
Phosphorylated MCC 20 46 V-0 / 15.4 10
/ Cellulose fiber In situ grafting 100 6 / 19 / 4.1 Zhang et al.106
Cellulose/Zn 95/4.96 59 / 30 66.6 33.6
PLA / Bulk 0 87 / / / / Costes et al.107
Kraft lignin (melt-blending) 20 40 / / 21 17
Organosolv lignin 20 27 / / ;33 19
Kraft lignin-PONH4 20 85 V-0 / ;40 10
Organosolv lignin- 20 85 V-0 / 30-33 12
PONH4
PLA / Bulk / / / 20.0 / 0 Chen et al.108
Chitosan/APP (melt-blending) 7/0 / V-2 24.3 / 0.6
Chitosan/APP 2/5 / V-0 33.1 17.4 4.1
PLA / Layer-by-layer / 48 6 2 / 22.0 / 0 Battegazzore et al.109
Chitosan (LbL) assembly 9 36 6 7 / 21.7 6 0.3 ;50.9 761
Chitosan/sepiolite/APP 3/5/2 33 6 5 / 25.3 6 0.3 ;61.1 861
(continued)
7
 8

Table 1. (continued)

Biopolymer Flame retardant Method of FR loading TTI UL-94 LOI pHRR Char Ref.
matrix application (Wt.%) (s) (%) (%) residue (%)

PLA / Reactive / / / 19.5 / 3.31 Ye et al.110

Chitosan/PLA/ melt-spinning 1 / / ;43 / 7.98
melamine phosphate
ester
Chitosan/PLA/ .2.5 / / ;43 / 0.92
melamine phosphate
ester
PLA / Bulk / 37 6 2 / 20.0 / 0 Zhang et al.111
Casein (melt-blending) 20 29 6 2 V-0 32.2 6 0.4 ;17.9 4.3
PLA / Electrostatic / / / 20.0 / / Zhong et al.112
Phytic acid (PA)/ self-assembly 2 / V-0 29 / /
nicotinamide
PLA / Reactive—bulk / 64 V-2 20.0 / 0.56 Liao et al.113
Tannic acid/APP (melt-blending) 5 52 V-0 27.0 6 0.1 ;8.6 7.78
Journal of Fire Sciences 00(0)
Mhlabeni et al. 9

cotton, hemp, flax, and wood. Cellulose is a linear polysaccharide composed of D-glucose
units linked by b-1, 4-glycosidic bonds.115,116 The glucose units are arranged in a linear
chain, allowing the formation of hydrogen bonds between hydroxyl groups on adjacent
chains. This results in a highly crystalline structure, which contributes to cellulose’s strength
and insolubility in water.114,116 The hydrogen bonding leads to the formation of microfibrils,
which are bundles of cellulose chains that provide structural integrity to plant cell walls.117
Cellulose derivatization involves substituting some of the hydroxyl groups on the cellu-
lose chain with other functional groups.116 Common derivatives include cellulose acetate,
cellulose nitrate, and carboxymethyl cellulose (CMC). Cellulose derivatization involves mod-
ifying cellulose to alter its properties, making it more suitable for plastic production. This
process improves solubility and thermoplasticity. Plasticization involves adding plasticizers
to cellulose derivatives to improve their flexibility and processability.118 Plasticizers are
mixed with cellulose derivatives to reduce intermolecular forces, allowing the material to
flow and be molded when heated. This process turns rigid cellulose derivatives into flexible,
workable plastics. These cellulose-based materials offer a sustainable alternative to conven-
tional plastics, aligning with growing environmental concerns and the demand for biode-
gradable products.
Cellulose has a low fire resistance, indicated by a limiting oxygen index of 19%.119
However, its ability to produce thermally stable charred residues when exposed to fire is an
advantage for its use in flame-retardant systems.120 During combustion, particularly under
conditions of limited oxygen, cellulose thermally degrades into char, gases, and volatile com-
pounds. The phenomenon of char formation during the burning of wood is well documen-
ted.120 Due to this property, cellulose is considered a suitable flame-retardant filler for
biopolymer-based applications.121 Table 5 summarizes the flame-retardant systems incor-
porating cellulose. The table provides quantitative data on the flame performance metrics to
illustrate the enhanced effectiveness. The data include key parameters such as TTI, UL-94
rating, LOI, PHRR, and char yield.
Various modifications have been proposed to enhance the flame-retardant properties of
cellulose-containing flame retardants. Modifications of cellulose often involve chemical
treatments via surface treatment or polymer/cellulose grafting.122 Phosphorylation of cellu-
lose is another well-established method to enhance flame retardancy of cellulose-based flame
retardants.123,124 Phosphorylation involves introducing phosphate groups into the cellulose
structure.125 Phosphorylation can enhance the flame retardancy of cellulose materials by
promoting char formation, reducing flammability, and increasing thermal stability.126
Research by Dahiya and Rana highlighted that phosphorus-containing cellulose significantly
improves char production.104 Costes and co-workers105 explored compositions involving
phosphorus-containing cellulose for sustainable flame-retarding PLA. In the study, phos-
phorus groups were either chemically grafted onto cellulose fibers, which were then incorpo-
rated into the PLA matrix, or PLA was blended with cellulose phosphorylated using a bio-
based phosphorus agent, such as aluminum phytate. Both methods resulted in enhanced
charring effects in cellulose. This modification aligns with the growing demand for sustain-
able and non-toxic flame-retardant solutions, making phosphorylated cellulose a valuable
material for a wide range of applications.
In their study, Feng and co-workers98 introduced an innovative method by chemically
grafting a phosphorus–nitrogen-based flame retardant onto the surface of cellulose nanofi-
bers (CNF) in situ for use in PLA. Their study revealed that incorporating 10 wt.% of the
phosphorus–nitrogen flame retardant on CNFs into PLA enabled the material to achieve a
10 Journal of Fire Sciences 00(0)

Figure 1. Mechanisms of ZnO-coated cellulose nanocrystals (CNC)/polymer char microstructure.121

V-0 flame resistance rating in vertical burning tests. In addition, it significantly reduced the
pHRR in cone calorimetry tests, indicating a marked decrease in flammability. The tensile
strength of PLA also increased by about 24%, reaching approximately 72 MPa. This work
provided a novel approach to creating advanced green polymeric materials by combining
exceptional flame retardancy with mechanical enhancement into a single hierarchical nano-
structured additive system.
Combining cellulose with nanoparticles can be utilized to enhance the flame retar-
dancy.127,128 Recent studies have demonstrated that treating cellulosic materials with nano-
sized zinc oxide (ZnO) can significantly enhance the flame retardancy of base polymers.103
This approach offers a promising route to improve the fire resistance of cellulose-based
flame retardants. Kabir and co-workers121 proposed a mechanism illustrating the fire retar-
dancy of ZnO-modified cellulose nanocrystal (CNC)-based polymers, shown in Figure 1.
ZnO is known for its thermal stability and ability to catalyze char formation, while CNCs
are highly crystalline and have a high surface area, making them effective as reinforcing
agents and promoting char formation.103,129 The mechanism illustrates how the combination
of these materials enhances the suppression of volatile emissions and char formation provid-
ing both solid- and gas-phase fire-retardant actions.121

Lignin. Lignin has been explored as a sustainable flame-retardant additive for PLA and other
biopolymers.130 Lignin is the second-most-abundant biopolymer after cellulose.131,132 Lignin is
rich in phenolic units and has a highly cross-linked structure.107 Its potential as a flame retar-
dant is attributed to its high char-forming capability.133 Lignin serves as a carbon source in the
condensed phase, promoting char formation, and quenches free radicals in the gas phase via
phenolic groups; however, these mechanisms depend on lignin’s origin, structure, and concen-
tration.134,135 Costes and co-workers107 studied the fire properties and thermal behavior of
Mhlabeni et al. 11

PLA/lignin composites containing 20 wt.% of both unmodified and modified lignin. The
results were evaluated using cone calorimetry, UL-94 tests, and thermogravimetric analysis
(TGA). Indeed, the TGA results demonstrated that incorporating untreated lignin into PLA
resulted in a flame-retardant effect primarily due to char formation. However, this also caused
a significant reduction in the thermal stability of PLA and a notable decrease in its TTI. This
means that while untreated lignin helped in forming a protective char layer, it also made PLA
more susceptible to thermal degradation and quicker to ignite. In contrast, lignin that was che-
mically treated with phosphorus (P) and nitrogen (N) showed more favorable results. The
treated lignin was effective in limiting the thermal degradation of PLA during both melt-
processing and TGA experiments. In addition, P-N-containing lignin significantly improved
the flame-retardant properties of the PLA composites, achieving a V-0 classification in the
UL-94 test. The results indicated that the PLA composite with P-N-modified-lignin not only
resists ignition but also self-extinguishes quickly when ignited.
Yang and co-workers also attained desirable flame retardancy for PLA/phosphorus-
nitrogen modified lignin composites, achieving a UL-94 V-0 rating and meeting industrial
standards.136 In their study, the phosphorus-nitrogen-modified lignin was embedded into
PLA through condensation reactions. A study by Zhang and co-workers137 has also demon-
strated the successful use of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)
and hexamethylene diisocyanate–modified lignin flame retardants in synthetic polymers.
The effectiveness of the lignin-based flame retardant was attributed to both its ability to
form an insulating char and the presence of phosphorus-nitrogen groups as modifiers.138 In
addition, because reactive flame retardants become a part of the polymer’s molecular struc-
ture, they are anticipated to have less of a negative impact on the polymer’s mechanical
properties. For instance, Zhang and co-workers139 synthesized a reactive flame retardant
using bio-derived multifunctional additives, including DOPO, diphenolic acid (DPA), and
phenylphosphonic dichloride (PPDC), compound abbreviated as PPD. The effectiveness of
the synthesized flame retardant was evaluated on the flame retardancy and mechanical prop-
erties of PLA. It was found that adding 6 wt.% PPD to PLA resulted in an LOI value of
27.1% and a pHRR of 388 kW/m2, compared to the PLA’s original values of 20.5% LOI
and 417 kW/m2 pHRR. In addition, the composite achieved a UL-94 V-0 rating, indicating
excellent flame retardancy, and demonstrated a significant increase in char residue yield.
The PLA/6% PPD composite also showed a 31% increase in impact toughness and a signifi-
cant improvement in tensile strength compared to the bulk PLA. The results were attributed
to fine and uniform dispersion of PPD within the resin matrix, along with strong interfacial
interactions. Similar observations have been reported for APP grafted onto lignin and PA
grafted onto bamboo charcoal through the in situ solid-phase polycondensation.140,141
Reactive flame retardants not only ensures long-term effectiveness but also addresses envi-
ronmental concerns associated with the leaching of flame retardants from the host polymer
matrices.142 This method is effective in mitigating potential environmental impacts and
improving sustainability of the flame-retardant polymers.
The study by Zhang and co-workers143 underlines the effectiveness of combining lignin,
microencapsulated ammonium polyphosphate (MAPP), and OMMTs in enhancing the
flame retardancy of PLA. Microencapsulation of flame retardants has proven to be an effec-
tive strategy in conjunction with melt-mixing.144–146 Microencapsulation of the flame
retardants allows for improved distribution and stability of the flame-retardant materials
within the polymer matrix.41,147,148 The study showed the combination of lignin, MAPP,
and organically modified MMT provided PLA with superior flame retardancy and thermal
12 Journal of Fire Sciences 00(0)

properties compared to systems without the combined components. This combination not
only improved the formation of a high-quality, durable char layer but also offered a sustain-
able approach to developing flame-retardant materials. The synergistic effect of these com-
ponents improved the overall fire resistance of the PLA.

Chitosan. CS has also been investigated as an effective charring agent because of its rich car-
bon, nitrogen, and hydroxyl functionalities.149,150 In flame retardancy applications, CS acts
primarily in the condensed phase, to form a more stable carbonous char layer.151,152
Battegazzore and co-workers109 used LbL assembly to coat CS to simultaneously improve
flame-retardant and mechanical properties of PLA biocomposites. The study demonstrated
reduced LOI values, substantial reduction in pHRR, and maximum average rate of heat
emission during cone calorimetry while maintaining the mechanical strength for the compo-
sites. In another study, Chen and co-workers108 incorporated CS alone and a combination
of CS/APP into PLA by melt-compounding. While the incorporation of CS alone into PLA
did not yield satisfactory flame-retardant performance, the CS/APP combination signifi-
cantly enhanced the flame-retardant properties of the composite. This was evidenced by
improved time of ignition, UL-94 ratings, higher limiting oxygen indices, and reduced heat-
release rates and total heat released in cone calorimeter tests. These findings underscore the
critical role of combining CS with phosphates in APP to achieve effective flame retardancy.
Reactive flame-retardant techniques have also been used to enhance CS-based flame retar-
dants. In a recent study, PLA and a melamine phosphate ester were grafted onto a CS
framework to create a flame retardant.110 Adding a small amount (\1%) of the CS-based
flame retardant to the PLA effectively enhanced both flame retardancy and mechanical
properties. However, it was also noted that an excessive amount (.1%) of CS-based flame
retardant led to a decline in mechanical performance. This highlights the importance of opti-
mizing the concentration of flame retardant to balance flame resistance and mechanical
integrity. Furthermore, a clear synergistic effect between CS and APP was observed, mean-
ing their combined effect on improving flame retardancy was greater than their individual
effects. A study by Zhang et al.153 demonstrated the effective performance of CS and algi-
nate, which were self-assembled with APP in an aqueous solution. At 10 wt.% loading of
APP/CS/AA into PLA, the LOI value increased to 30.6%, UL-94 V-0 rating was achieved,
and a 23.1% reduction in the pHRR was observed. Thermogravimetric infrared (TG-IR)
analysis supported that the flame-retardant action occurs mainly through a condensed-phase
mechanism, evidenced by reduced peak intensities of volatile degradation products. These
results indicated a suppressed release of flammable gases. This was attributed to both CS
and alginate acting as carbon agents. The mechanical testing showed an impact strength of
4.3 kJ/m2 and elongation at break of 9.8%, with a trade-off in tensile strength, decreasing to
46.4 MPa from 56.7 MPa for neat PLA. These results suggested effective flame retardancy
with a minor compromise in tensile strength. Indeed, this work highlights the potential of
using CS/alginate combination, although further improvements in mechanical properties
may be necessary for applications requiring high structural integrity. In addition, the study
provides limited insight into the detailed molecular interactions between the APP, CS, and
alginate. Finally, alginate systems tend to be more hydrophilic than CS, raising concerns
about the composite’s stability and flame retardancy under humid conditions.154,155
Addressing these limitations could provide a more balanced flame-retardant system with
improved practical applicability.
Mhlabeni et al. 13

Figure 2. Digital photographs of (a) PLA and (b) PLA/20 wt.% casein samples after the UL-94 tests at
different times.111

Casein and other proteins. Casein is a protein found in milk, and it consists of phosphorus-
nitrogen groups.156 Due to the known P-N synergistic effects in flame-retardant applica-
tions, casein has been explored as a flame-retardant filler.157 The casein flame-retardance
mechanism involves the release of non-flammable NH3, H2O to act in the gas phase, and
subsequent phosphorus-containing acids such as phosphoric acids that dehydrate the poly-
mer, leading to the formation of a stable char.158,159 Zhang and Jin explored casein as flame
retardant for PLA, and the results showed that incorporating casein into PLA significantly
enhanced PLA’s flame retardancy evidenced by higher LOIs.111 Furthermore, Figure 2 dis-
plays digital photographs of (a) PLA and (b) PLA/20 wt.% casein samples after the UL-94
tests at different times. The combustion of pure PLA showed significant burning flame with
melt-dripping and no formation of a protective char layer. On the contrary, the digital
photographs of the combustion of the PLA/20 wt.% casein provided clear visual evidence
of the enhanced flame retardancy through char formation, however, also with melt-dripping.
Although the addition of casein reduced tensile strength of the composite, the dripping
occurred due to decreased Tg as heating resumed. Conversely, the dripping helped extinguish
the flame, as it did not ignite the cotton. Thus, the PLA-casein composited achieved a V-0
rating, demonstrating effective flame retardancy. The study also predicted the proposed
casein dual-action flame-retardant mechanism in the gas and condensed phase. Supporting
thermogravimetric analysis coupled with fourier transfom infrared spectroscopy (TGA-
FTIR) analyses showed intense peaks (965 cm–1 and 930 cm–1 and 3332 cm–1), correspond-
ing to the NH3 gas at 268.8°C and 380.8°C, respectively, and two major peaks at 1596 cm–1
and 1256 cm–1 at 551°C corresponding to the P–C bond and the P–O–P groups,
14 Journal of Fire Sciences 00(0)

Figure 3. Synthesis route of soybean phosphorus-nitrogen-containing flame retardant (SPDP) and the
flame retardancy mechanism.160

respectively. While the results are promising, the reduced TTI in the PLA/casein composite
suggests reduced thermal stability. This shortcoming may limit casein’s effectiveness in cer-
tain high-heat applications and impact the durability of the flame retardancy over time. This
highlights the need for further modification of the casein to improve fire performance with-
out compromising material stability.
Dong and co-workers also made significant progress in developing a bio-based flame
retardant using soybean protein.160 Their study investigated a dimethyl phosphate–modified
soybean protein abbreviated as SPDP. Figure 3 illustrates both the synthesis process of
SPDP and its flame-retardant mechanism in PLA. The study also predicted that SPDP pro-
vides a dual-action approach to fire prevention. The proposed mechanisms occurred through
char formation and gas-phase dilution. Upon combustion, SPDP releases phosphorus-
containing acids, such as phosphonic acid, polyphosphate, or metaphosphate, which contrib-
ute to dehydration and char formation. Subsequently, the protein releases NH3, a non-
flammable gas. The released NH3 helps dilute the concentration of flammable gases around
the PLA. While Dong and co-workers made great progress, some aspects could be further
explored to solidify their findings. For example, the study suggested the mechanism via NH3
gas-phase dilution, however, lacks comprehensive kinetic analysis to support these conclu-
sions. Indeed, the release of NH3 is proposed as beneficial, yet quantifying the actual concen-
tration and the impact of NH3 could enhance the understanding of its role in diluting
flammable gases.

Phytic acid. PA is considered an eco-friendly, bio-based alternative in flame retardancy, due

to its phosphorus and hydroxyl groups.100 PA’s role in flame-retardant system involves the
release of phosphoric acid or other phosphorus compounds, thereby interrupting the free
radical combustion reaction while promoting char formation.161,162 Xu and co-workers163
Mhlabeni et al. 15

synthesized a fire retardant combining PA and arginine (AR) in aqueous phase. Upon the
addition of 1 wt.% PA-AR, the LOI value of PLA reached 26.8% and UL-94 V-0 rating. In
a more recent study by Zhong and co-workers,112 the combination of PA and nicotinamide
as flame retardants for PLA showed improved flame retardancy for PLA. The addition of
just 2 wt.% of PA and nicotinamide increased the LOI of PLA to 29.0% and gave a UL-
94 V-0 rating. Xiong and co-workers99 explored a greener strategy for synthesizing PA/CS
bio-based flame retardants for PLA.164 The study employed water as the solvent for the LbL
method. TG-IR analysis demonstrated that this system effectively suppresses the release of
volatile components during degradation, as evidenced by weaker absorption intensities. The
barrier effect of the char formed suggested the condensed-phase mechanism was predomi-
nantly responsible for reducing combustible gas emissions. On the other hand, although
elongation at break increased from 8.1% to 10.4%, this might not fully compensate for the
loss in tensile strength, 56.7–45.3 MPa, especially in scenarios where high strength and flexi-
bility are both crucial. Finally, the lack of comparison to similar water-based LbL assembly
methods leaves a gap in understanding how this approach performs relative to other envir-
onmentally friendly flame retardants.

Tannic acid. Tannic acid (TA) is a natural catechol derivative, known to exhibit strong anti-
oxidant properties due to its numerous phenolic hydroxyl groups.165 In the flame retardancy
mechanism, TA helps reduce the production of free radicals through its rich phenolic struc-
ture while releasing active phenolic radicals.166,167 TA is also said to promote the formation
of a stable char layer during combustion.168 However, TA is less effective on its own as an
intumescent flame retardant.169 So, TA is typically combined with other compounds to
enhance its flame retardancy. Several studies have explored various combinations of TA
with other substances to improve the flame retardancy of PLA.113,169,170 Qiu and co-workers
developed a bio-based flame-retardant additive synthesized from TA, CS, and PA.168 This
flame retardant was created using a free radical grafting process followed by electrostatic
adsorption. When a low addition of 3% PA/TA -CS was introduced into PLA via melt-
blending, the resulting composite exhibited significant flame retardancy, achieving an LOI
value of 26.9% and a UL94 V-0 rating. Laoutid and co-workers169 prepared three combina-
tions of TA with OMMT, metallic phytate salt, and by chemical modification of TA through
grafting phosphoric acid groups. Another study by Laoutid and co-workers170 explored the
antioxidative properties of a combination of TA and PA with polyethyleneimine (PEI), ser-
ving as a binding agent. Liao and co-workers113 developed a novel integrated intumescent
flame-retardant system that contained APP as the core material, with PEI serving as a brid-
ging agent to connect APP and TA. Overall, these studies found a significant improvement
of the flame retardancy of PLA biocomposites, as evidenced by higher LOI values, successful
UL-94 V-0 classification, and a reduced pHRR. These improvements highlight the effective-
ness of using TA as flame-retardant additives in PLA-based materials. These combinations
were aimed at leveraging the synergistic effects of these materials to improve the flame retar-
dancy of PLA.

Bio-based flame retardants for PBS

PBS is a biodegradable aliphatic polyester gaining attention as a promising alternative to tra-
ditional petrochemical-based plastics. This is due to its biodegradability and renewable
16 Journal of Fire Sciences 00(0)

sourcing options. PBS is composed of repeating units of butylene succinate, forming a linear
polyester chain.98 PBS can be synthesized from petrochemical-based succinic acid and 1,4-
butanediol and from biomass fermentation processes. PBS can be processed using conven-
tional plastic processing techniques such as injection molding, extrusion, and thermoform-
ing.171 It can be easily blended with other polymers or additives to modify its properties and
improve performance.172 It is reasonable to predict that with the increasing applications of
biopolymers, flame retardancy of PBS will play an essential role in its demand. Table 2 sum-
marizes the flame-retardant systems that have been applied to PBS. The table provides quan-
titative data on the flame performance metrics to illustrate the enhanced effectiveness. The
data include key parameters such as TTI, UL-94 rating, LOI, pHRR, and char yield.

Lignin. Lignin has been explored as a sustainable flame-retardant additive for PBS.173
Recently, Wang and co-workers173 observed a positive effect on flame retardancy using che-
mically untreated cellulose- and lignin-based fillers, eucommia residue (ER), which con-
tained 18 wt.% cellulose, 13 wt.% hemicellulose, and 35 wt.% lignin. The ER was explored
as a flame retardant for PBS in PBS/ER composites, with ER loadings ranging from 5% to
30%. The proposed reinforcing mechanism involved the condensed aromatic structures of
lignin, which led to increased char formation, exerting a barrier effect. In addition, it was
suggested that the cellulose- and lignin-based fillers effectively suppressed the smoke release
behavior of PBS. This suppression was attributed to the increased carbon residue content,
which reduced the release of aromatic or other small unstable carbon particles produced
during combustion.
Ferry et al.175 and Chen et al.174 prepared phosphorus-nitrogen-modified lignin/PBS
composites by melt-mixing and grafting, respectively. In their studies, lignin enhanced the
char residue, contributing to the material’s flame-retardant properties. Moreover, the phos-
phorylation of lignin made it a particularly effective bio-based flame-retardant compo-
nent.138,174,175 Figure 4 shows the cone calorimetry results by Chen and co-workers174 after
adding 10%, 20%, and 30% by weight of a phosphorus–nitrogen-containing lignin (CP-lig-
nin) fire retardant into PBS. The PBS/lignin composite had a significantly lower pHRR and
total heat release (THR) than neat PBS. Likewise, the composites produced more char, as
observed in Figure 4. The increase in the amount of char enhanced the material’s ability to
delay flammable gas transfer and resist burning, thus improving its flame-retardant
properties.

Nanoparticles. It is well known that mineral/inorganic nanoparticles enhance the barrier

properties and heat resistance of polymers. Boehmite (Bhm) nanoparticles, for instance, sig-
nificantly improved the flame retardancy of PBS at 2 wt.% filler content.176 Other nano-
flame retardants, that is, carbon black, nano-clay, HNTs, carbon nanotube, have also been
used to improve the pHRR and limited oxygen index value and to inhibit/reduce melt-
dripping of PBS.31,177,178,180,181 The mechanism of action of these nano-flame retardants
involved hindering/delaying the diffusion of oxygen and heat into the interior substrate,
which not only delayed melt-dripping but also contributed to the formation of a more stable
charred layer.182,183
Some claims have been made regarding the synergistic effect between phosphorus-based
and nanoparticle flame retardants.184 The study by Kong and co-workers179 highlights the
combined effects of a bio-based phytic acid arginine salt (PaArg) and hydroxylated MMT
Table 2. Bio-based flame-retardant systems applied on PBS and their effectiveness

Biopolymers Flame retardant Method of FR loading TTI UL-94 LOI pHRR Char Ref.
matrix application (Wt.%) (s) (s) (%) residue
(%)
Mhlabeni et al.

PBS / Bulk 30 96 / / / 1.2 6 0.3 Wang et al.173

(melt-blending)
Lignin/cellulose 42 6 3 / / 43.2 7.3 6 0.9
PBS / Grafting—Bulk / 43 6 1 / / / 0.1 6 0.1 Chen et al.174
(melt-blending)
Phosphorus- 30 31 6 1 / / / 9.6 6 0.1
nitrogen lignin
PBS / Additive / 72 / / / 5.7 Ferry et al.175
melt-blending
Grafting
Alkali lignin 20 42 / / 49.0 17.0
Phosphorus-alkali 20 40 / / 52.0 14.8
lignin
PBS / Reactive—bulk / / / 21.28 / 4.9 Kahkesh and Rafizadeh176
(melt-blending)
Boehmite 2 22.85 / 10.3
nanoparticles
PBS / Bulk / 63.3 6 1.5 / / / 0.12 Mokhena et al.177
(melt-blending)
Expanded graphite/ 6/3 50.0 6 5.3 / / 40.5 8.55
clay nanoparticles
PBS / Bulk / 48 6 1 / 21.0 / 0.1 6 0.1 Chen et al.178
(melt-blending)
Nano-sized carbon 10 39 6 3 / 28.5 61.6 11.7 6 0.2
black
(continued)
17
 18

Table 2. (continued)

Biopolymers Flame retardant Method of FR loading TTI UL-94 LOI pHRR Char Ref.
matrix application (Wt.%) (s) (s) (%) residue
(%)

PBS / Bulk / 50 / 24.5 / 3 Wang et al.31

(melt-blending)
Halloysite 1.5/28.5 40 V-0 58.2 81.4 32
nanotubes/(APP/
melamine/
pentaerythritol)
PBS / Bulk 25 46 / 20.8 / 0.1 Kong et al.179
(melt-blending)
Phytic acid arginine 23.5/1.5 22 V-2 26.4 41.4 13.4
salt
Phytic acid arginine 25 V-0 31.4 74.1 15.3
salt/nano-
montmorillonite
Journal of Fire Sciences 00(0)
Mhlabeni et al. 19

Figure 4. (a) HRR and (b) THR versus time curves, and cone calorimeter digital photos of (c) PBS,
(d) PBS/10 wt.%-CP-lignin, (e) PBS/20 wt.%-CP-lignin, and (f) PBS/30 wt. %-CP-lignin.174

(abbreviated as DK2) for PBS. Figure 5 serves as a visual summary of the proposed
mechanism of action for the synergistic effect between the bio-based PaArg/DK2 for PBS.
The mechanisms and synergistic effects involved the phosphorus, from PA, catalyzing the
charring process and acting in the gas phase (as HPO and PO) to quench free radicals.
Upon the addition of MMT, the clay layers reinforced the char structure by increasing the
viscosity of the polymer melt, reducing the gas-release rate and forming a filler-packed
foam-like structure. The study highlighted an improvement in flame retardancy including
20 Journal of Fire Sciences 00(0)

Figure 5. Mechanism and synergistic effects of PBS/PaArg/DK2.179

LOI enhanced to 31.4%; notable reductions in pHRR, THR, and smoke production; and a
V-0 rating. However, the mechanical properties of the composite require closer examination.
The measured tensile strength, bending strength, and impact strength of the composite have
all been compromised compared to pure PBS. Thus, while the study contributes to the devel-
opment of bio-based flame retardants, further research could strengthen the evidence for the
claimed synergy. In addition, as the MMT is proposed to reinforce the char structure and
increase melt viscosity, further data, such as rheological analysis, could better substantiate
this claim.

Bio-based flame retardants for PHB

PHB is a biodegradable thermoplastic polymer produced by various microorganisms as an
energy storage compound. PHB is a polyester composed of 3-hydroxybutyrate monomers.101
The monomers are linked by ester bonds, forming a linear polymer chain.185 It is part of the
polyhydroxyalkanoates (PHA) family and is of great interest for sustainable and environ-
mentally friendly applications. PHB can be processed using conventional plastic-processing
techniques, such as injection molding, extrusion, and thermoforming. However, its narrow
processing window requires precise temperature control to prevent thermal degradation.171
In addition, PHB is inherently flammable, which significantly limits its applications, espe-
cially where fire safety is a concern.186 By incorporating flame retardants, using natural fil-
lers, and employing advanced polymer design techniques, PHB can be tailored to meet the
fire safety requirements of various industries. Table 3 summarizes the flame-retardant sys-
tems that have been applied to PHA. The table provides quantitative data on the flame per-
formance metrics to illustrate the enhanced effectiveness. The data include key parameters
such as TTI, UL-94 rating, LOI, pHRR, and char yield.
Table 3. Flame-retardant systems applied on PHAs and their effectiveness
Mhlabeni et al.

Biopolymers Flame retardant Method of application FR loading TTI UL-94 LOI pHRR Char Ref.
matrix (Wt.%) (s) (%) (%) residue
(%)

PHBV/PBAT / Bulk (melt-blending) / 22 / / / / Gallo et al.187 and

Kenaf fibers 30 25 / / 50 9.9 Russo et al.188
PHB / Bulk (melt-blending) / 45 6 3 / 23.9 / 0.0 6 0.1 Battegazzore et al.189
Hemp hurd (HHC) 30 30 6 1 / 20.1 33 6.5 6 0.1
fibers
Alfalfa (AA) fibers 30 29 6 1 / 20.8 32 7.8 6 0.1
PHA PHA In situ intercalation— / 15 V-0 19.8 / 7.3 Xu et al.94
bulk (melt-blending)
Hyperbranched 15 10 29.6 / 13.8
macromolecules/
bentonite
P(3HB-co-4HB) / In situ intercalation— / 55 6 1 / / / 4.3 6 0.4 Wu et al.190
bulk (melt-blending)
Rice husk ash 5 48 6 2 / / 13.8 11.7 6 0.5
Alkali lignin/rice 10/5 35 6 4 / / 18.0 15.4 6 0.3
husk ash
Melamine 30/5 83 63 / / 42.8 24.3 6 0.8
phosphate lignin/
rice husk ash
21
22 Journal of Fire Sciences 00(0)

Figure 6. Complex viscosity (h*) of PHB and PHB-based composites.189

Natural fibers. Natural fibers from various sources have been effectively utilized to improve
the flame-retardant properties of PHA copolymers, specifically poly(3-hydroxybutyrate-co-
3-hydroxyvalerate) (PHBV), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-
co-4HB).187,188 The referenced studies investigated the kenaf fibers that are composed of
cellulose, lignin, hemicelluloses, and a small amount of ash. The hydroxyl-rich kenaf fibers
exhibited a beneficial effect as a carbonization agent, contributing carbon-rich content that
aids in the formation of a char layer. Nonetheless, it is important to note that, natural
fibers fall short in some instances. Battegazzore and co-workers189 conducted a study on
poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH abbrevated as PHB on thier study)
copolymers that were prepared by melt-blending with hemp hurd (HHC) and alfalfa (AA)
fibers. The study found that the addition of both types of natural fibers into the PHBH
copolymers resulted in composites with higher viscosity than neat PHBH as illustrated in
Figure 6. The increased viscosity was a physical consequence from the added resistance to
flow of the filler within the melt. The study argued that higher viscosity was beneficial for
flame retardancy as it helped prevent dripping during combustion. This is crucial in prevent-
ing the spread of fire, as drips can ignite other materials. In analyzing their data from the
cone calorimetry tests, these natural fibers significantly aided the reduction of the HRR.
However, their findings also revealed that the presence of these HHC and AA fibers reduced
the LOI value and TTI of PHBH. In addition, challenges in completely preventing the
spread of flames by the formed char under UL-94 tests were still present. This suggests that
the natural fibers made the PHB more flammable, as TTI is decreased, and less oxygen is
needed to sustain combustion. This observation contradicts with the benefits of increased
viscosity melt as a means for slowing down the diffusion of volatile degradation products
and aids in the development of a stable char layer. In addition, it should be noted that when
viscosity is too high, it can hinder processability and impede proper mixing and dispersion
of fillers within the polymer matrix. Improper mixing and poor dispersion of fillers can
potentially lead to inhomogeneous material properties. Therefore, when designing flame-
retardant composites, balancing the polymer melt viscosity with flame retardancy is crucial.
The goal is to have enough viscosity to improve flame retardancy without compromising
processability or overall material performance.
Mhlabeni et al. 23

Table 4. The results of vertical combustion for PHA/HBM-BNT composites94

PHA/HBM-BNT (wt.%) LOI (%) t1, t2 (s) Dripping Cotton ignition Rating

0 19.8 6 0.3 5, 4 Serious Yes V-2

5 27.3 6 0.4 2, 19 Serious Yes V-2
10 28.5 6 0.2 3, 14 Light Yes V-1
15 29.6 6 0.5 2, 4 Light Yes V-0

Nanoparticles. Enhancing the flame retardancy of PHAs through phosphorylation of nano-

clay flame retardants is also an emerging area of research.191 Xu and co-workers94 proposed
an innovative method involving the intercalation of phosphorus-nitrogen-containing hyper-
branched macromolecules (HBMs) between bentonite (BNT) layers (HBM-B). The study
reported significant improvements in the flame retardancy of PHA, poly(3-hydroxybuty-
rate-co-3-hydroxyhexanoate). The addition of 15 wt.% HBM-B resulted in an LOI increase
of up to 29.6% from 19.8%. The same composite achieved a V-0 rating in the UL-94 verti-
cal burning test. Table 4 shows the results obtained from LOI and UL-94 tests for the com-
posites. Furthermore, the study reported substantial reductions in heat release rate, total
hear release, and total smoke production (TSP), along with a significant increase in char
residue yield, during cone calorimeter tests (Figure 7). The pHRR of PHA decreased from
981.9 kW/m2 to 874.1 kW/m2 with the addition of HBM-B. Similarly, the THR decreased
from 104.2 MJ/m2 to 94.1 MJ/m2. While the reductions in pHRR and THR observed with
the addition of HBM-B do indicate improvements in flame retardancy, the extent of the
decrease is limited. Perhaps, further enhancements could be pursued to maximize flame-
retardant performance. For the same composite, the TSP reduced indicating that fewer vola-
tile compounds are released during combustion. It may be beneficial to assess the presence
and concentration of toxic gases in the combustion products. This may provide a more com-
prehensive evaluation of fire safety beyond just the TSP values.
Wu and co-workers190 investigated the synergistic effects of melamine phosphate modified
lignin (MAP-lignin) and rice husk ash (RHA) on the flame-retardant properties of P(3HB-co-
4HB). Rice husk contains mainly amorphous silica ash after burning.192 Using RHA as a flame
retardant is considered environmentally friendly, as it utilizes an agricultural waste product.
The study found that the addition of 30 wt.% MAP-lignin and 5 wt.% RHA significantly
improved the pHRR and THR of P(3HB-co-4HB) in cone calorimeter tests. In addition, the
study included morphological and microstructural analysis of char residues obtained from the
cone calorimeter tests using scanning electron microscopy with energy dispersive X-ray (SEM-
EDX) analysis. The micrographs from this analysis are shown in Figure 8. The deduction was
that in the presence of phosphorylated lignin, the composite exhibited a more compact and
coherent structure. This morphology indicates a more effective barrier against heat and mass
transfer. This was observed with an increase in carbon content up to 41 wt.%, attributed to
higher char formation, and the presence of 9 wt.% phosphorus.

Bio-based flame retardants for starch-based plastics

Starch is a natural polymer abundant in various plants and is primarily extracted from corn,
potatoes, wheat, and rice.193,194 Starch is a polysaccharide composed of glucose units.195 It
24 Journal of Fire Sciences 00(0)

Figure 7. (a) HRR, (b) THR, (c) TPS, and (d) Residual mass of PHA and PHA/15 wt.% HBM-B obtained
from cone calorimetry.94

consists of two main components: amylose and amylopectin.196 Amylose is a linear polymer
of glucose units linked by a-1, 4-glycosidic bonds. Amylose typically makes up 20%–30% of
starch and is responsible for the crystalline structure of starch granules.197,198 Amylopectin is
a branched polymer with a-1, 4-glycosidic bonds and a-1, 6-glycosidic linkages at the branch
points. Amylopectin constitutes 70%–80% of starch and contributes to the amorphous
regions of starch granules.193,197 Starch occurs naturally in the form of granules, which vary
in size and shape depending on the plant source.199 These granules are semi-crystalline, with
alternating crystalline and amorphous regions.
Thermoplastic starch (TPS) is a biodegradable material derived from starch.200 To trans-
form starch into a thermoplastic material, it is mixed with plasticizers, typically water, gly-
cerol, or sorbitol.201 This process disrupts the hydrogen bonds in the starch granules,
allowing the material to flow when heated and be molded into different shapes. TPS is
produced through thermal processing methods such as extrusion or injection molding.
During this process, the plasticizers and heat facilitate the gelatinization and melting of
starch, creating a homogeneous, flexible material.202 Other additives like compatibilizers,
fillers, and reinforcing agents can be incorporated to enhance the mechanical properties and
processability of TPS.203–205 TPS offers a sustainable and biodegradable alternative to
Mhlabeni et al. 25

Figure 8. SEM images of char residues after cone calorimeter measurements: (a) P(3HB-co-4HB)/RHA,
(b) P(3HB-co-4HB)/10 wt.% alkali lignin, and (c) P(3HB-co-4HB)/10 wt.% MAP lignin.190

traditional plastics, leveraging the abundant and renewable nature of starch. Table 5 sum-
marizes the flame-retardant systems that have been applied to starch. The table provides
quantitative data on the flame performance metrics to illustrate the enhanced effectiveness.
The data include key parameters such as TTI, UL-94 rating, LOI, pHRR, and char yield.

Phytic acid and nanoparticles. TPS is a plant-based biopolymer that is highly flammable and
hygroscopic. In the development of fully biodegradable starch-based materials, the incor-
poration of flame retardants must be carefully managed to ensure both effectiveness and bio-
degradability. The incorporation of choline phytate (CPA) into TPS significantly enhanced
the flame-retardant properties of the composite.206 This was evidenced by improved UL-94
ratings, higher limiting oxygen indices, and reduced heat release rates and total heat released
in cone calorimeter tests.
Intumescent formulations consisting of oxidized starch (OS) as a carbonization agent,
APP, and PLA were successfully prepared using a twin-screw extruder.207 These formula-
tions exhibited enhanced flame retardancy evidenced by improved heat release rate, THR,
TTI, and residual mass percentage. The mechanism behind these improvements was attrib-
uted to the effective char formation promoted by CPA and APP ring combustion,
respectively.
The research by Liu et al.208 also highlights a promising approach to enhancing the flame
retardancy of TPS by leveraging the synergistic effects between PA and HNTs. This
 26

Table 5. Dual function of thermoplastic starch in flame retardant systems and their effectiveness

Biopolymers Flame retardant Method of application FR loading TTI UL-94 LOI pHRR Char Ref.
matrix (Wt.%) (s) (s) (%) residue
(%)

Thermoplastic Choline phytate Bulk (melt-blending) 30 / V-0 43.7 / / Wang et al.206

starch (TPS)
PLA / Bulk (melt-blending) / 80.2 6 0.9 / / / 0.0 Maqsood and
Oxidized starch/ 1/10 65.5 6 2.6 / / 39.0 15.1 6 0.5 Seide207
APP
Oxidized starch/ 7/10 50.4 6 3.4 / / 52.0 33.5 6 0.9
APP
TPS / Reactive—Bulk / / / 19 / 12.9 Liu et al.208
(melt-blending)
Phytic acid 10 / / 34 65.6 20.2
Journal of Fire Sciences 00(0)
Mhlabeni et al. 27

combination not only improves fire resistance but also maintains the material’s eco-friendly
attributes, making it a valuable strategy for developing safer, more sustainable polymer
composites.

Discussion of results
The development of effective flame retardants for biopolymers is crucial for expanding their
applications in areas requiring fire safety. The global flame-retardant market was valued at
USD 8.63 billion in 2022, with a projected compound annual growth rate (CAGR) of 7.1%
from 2023 to 2030. APP and metallic hydroxides, for example, MH and ATH, are among
the most effective conventional flame retardants.209–211 Furthermore, these flame retardants
are also cost-effective compared to other halogen-free systems. However, despite their advan-
tages, APP, MH, and ATH show limited efficiency as flame retardants when used alone in
some biopolymers, such as PLA and PBS.212–215 Moreover, metallic hydroxides are known
to require higher loading amounts in polymers. This ensures compromised mechanical prop-
erty and processability. Accordingly, when used in PLA, phosphorus-containing flame retar-
dants, including APP, are often part of intumescent formulations.216 Typically, 20%–30% of
such flame retardants are required to raise PLA’s flame retardancy from a non-classifiable
state to a V-0 rating, with an increase in LOI to 38.217 Synergistic combinations of APP with
inorganic particles, such as melamine (MEL), MMT, aluminum hypophosphite (AHP), or
multi-wall carbon nanotubes (MWCNT), have also demonstrated significant improvements
in flame retardancy.218–220
While considerable progress has been made, ongoing research is focused on enhancing the
flame-retardant efficacy and environmental safety. This review consolidates the current state
of bio-based flame-retardant strategies for biopolymers, highlighting their mechanisms, effec-
tiveness, and challenges. This shift toward bio-based solutions not only supports environ-
mental sustainability but also addresses the growing need for greener alternatives in flame
retardancy. Indeed, improved fire performance can be achieved using bio-based flame retar-
dants, which also offer the benefit of reduced environmental impact. In most cases, bio-based
additives, such as lignin, cellulose, PA, CS, TA, among others, have a charring ability when
burnt or promote char formation. The char formed acts as a protective barrier, reducing heat
transfer and slowing down the degradation of the underlying material, thereby enhancing
flame retardancy. Due to this property, these typical additives have potential applications in
the development of sustainable flame-retardant biopolymer composites. However, important
concerns remain that warrant further investigation.
Similar to conventional methods, one major concern is the low effectiveness of bio-based
flame-retardant fillers when used alone. Their effectiveness is significantly enhanced through
modifications with phosphorus-based or/and nitrogen-based compounds, or by combining
them with nanomaterials.86,107,108,174,179,190 In addition, advanced preparatory methods like
a combination of grafting and melt-blending or LbL assembly are used to further improve
their performance.105,109,208 Figure 9(a) and (b) shows data reproduced from the referenced
studies to highlight these improvements. However, some shortcomings have also been
reported due to the nature of the filler or its weight percentage composition.110,111,174 These
shortcomings are often characterized by a decreased TTI (Figure 9(c) and (d)).174,175,179,207
Compromised TTI is an alarming drawback in flame-retardant applications. When the TTI
is compromised, it means the material ignites more quickly than desired, reducing its overall
28 Journal of Fire Sciences 00(0)

Figure 9. Effectiveness of (a) lignin & (b) chitosan on PLA, and (c) phytic acid & (d) lignin on PBS
flame-retardant fillers before and after modification/combination with modifiers. Data reproduced with
permission from Costes et al., Chen et al., and Kong et al.107,108,174,179

effectiveness. This could happen due to the specific composition of the flame retardant, the
nature of the filler used, or its interaction with the polymer matrix. Another area of concern
is the lack of complementary results in mainstream research studies. It is often believed that
some studies focus only on cone calorimetry, while others emphasize LOI or TGA, or UL-
94 V-rating, leading to an incomplete understanding of overall fire performance of the com-
posite.103,176,207 Addressing these gaps and concerns through comprehensive, multi-faceted
research will be critical in advancing the field of bio-based flame retardants for biopolymers.
Bio-based flame retardants may be somewhat more expensive than conventional flame
retardants. This price disparity can be attributed to factors common to many
Mhlabeni et al. 29

environmentally friendly alternatives, where healthier and more sustainable solutions often
come with higher costs. However, the use of renewable and greener processes in the produc-
tion of bio-based flame retardants can help salvage some of the cost disadvantages. These
eco-friendly methods not only promote sustainability but also reduce reliance on non-
renewable resources, which can lead to long-term cost benefits. In addition, much like con-
ventional flame-retardant systems, bio-based alternatives often require further modification
or combination with synergistic additives to enhance their effectiveness. These necessary
modifications add to the overall cost, although they are essential for achieving the desired
performance in fire resistance. However, as green chemistry and sustainable manufacturing
processes continue to advance, these costs could decrease over time, making bio-based flame
retardants a more competitive option in both environmental and economic terms.

Conclusion and future directions

The innovative approach to enhance the effectiveness of bio-based flame retardants, particu-
larly through phosphorylation, shows great promise. In addition, nitrogen-containing and
nano-structured compounds can act synergistically with carbon- and phosphorus-based
flame retardants to further improve fire resistance. As a result, renewable phosphorus-
containing and nitrogen-containing additives such as DNA, PA, TA, casein, and hydropho-
bins are potential candidates for biopolymers. This broad applicability highlights the poten-
tial of bio-based flame retardants to improve the fire safety of various biopolymeric
materials while maintaining environmental sustainability. Therefore, future research should
focus on conducting studies that simultaneously assess multiple aspects of flame retardancy,
including mechanical properties and comprehensive fire performance metrics. This will pro-
vide a more complete understanding of how different flame retardants perform in various
scenarios.
The effect of bio-based flame retardant on the biodegradability of biopolymers is another
key area to study. Flame-retardant additives could potentially alter the chemical structure
and physical properties of biopolymers, which might affect their ability to biodegrade under
natural conditions. Furthermore, in some cases, biodegradability is not a desired property,
particularly for applications requiring durability. Hence, it is essential to develop flame retar-
dants that maintain or enhance biodegradability without compromising the fire resistance of
the material. Developing flame retardants that are compatible with biopolymers and effec-
tive at low loadings may be a solution. It is important to emphasize that the effect of flame-
retardant additives on the biodegradation of biopolymers is yet to be thoroughly studied.
While flame-retardant additives are crucial for enhancing the fire resistance of biopolymers,
their impact on the material’s biodegradability remains unexplored. For this to be done, fur-
ther empirical studies and advanced characterization techniques are recommended.

Author contributions
Thobile L Mhlabeni: Conceptualization, Investigation, Methodology, Roles/writing—original draft,
Formal analysis, Writing—review and editing, and Validation. Endazenaw B Chemere: Writing—
review and editing, Validation. Tamba Jamiru: Writing—review and editing, Validation, Funding
acquisition. Washington Mhike: Conceptualization, Writing—review and editing, Validation,
Supervision, and Funding acquisition.
30 Journal of Fire Sciences 00(0)

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or
publication of this article: Open access funding provided by Tshwane University of Technology. The
authors received no direct funding for this research.

ORCID iDs
Thobile L Mhlabeni https://orcid.org/0000-0002-5698-0533
Washington Mhike https://orcid.org/0000-0003-4670-1171

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Author biographies
Thobile L Mhlabeni is a Postdoctoral Researcher at Tshwane University of Technology in Pretoria,
South Africa. She earned her Ph.D. in Chemical Engineering from the University of Pretoria in 2023.
Her current research centers on the development and application of advanced biofreindly nanostructured
and polymeric materials.

Endazenaw B Chemere is an Assistant Professor of Chemistry. He receveid two Ph.D degrees from
National Taiwan University of Science and Technology (NTUST) and Ming Chi University of
Technology (MCUT) in 2021 and 2022, respectively. Currently, he is a postdoctoral research fellow at
Tshwane University of Technology in Pretoria, South Africa.

Tamba Jamiru is an Associate Professor in Mechanical Engineering at Tshwane University of

Technology. His research focuses on mechanical nanomaterials, advanced composites and phase
transfomation, contributing to advancement in Materials science and Engineering.

Washington Mhike is a faculty member in Chemical, Metallurgical and Materials Engineering at the
Tshwane Universty of Technology. He earned his Ph.D. in Chemical Engineering from the University
of Pretoria in 2016. His research addresses scocietal challenges, focusing on malaria prevention,
polymeric applications in water treatment, compostable medical decices and eco-friendly flame
retardants.