Indian Journal of Fibre & Textile Research

Vol. 48, December 2023, pp. 475-494

DOI: 10.56042/ijftr.v48i4.7662

Review Article

Flame retardant finishing of textiles – A comprehensive review

Palak Kakar, Ankit Singh & Javed Sheikha
Department of Textile and Fibre Engineering, Indian Institute of Technology Delhi, New Delhi 110 016, India

Received 14 July 2022; revised received and accepted 1 June 2023

Flame retardant (FR) finishing is one of the most vital finishes required to develop flame retardant textiles for human
protection. Traditional flame retardants are based on halogen, phosphorus and phosphorus-nitrogen chemistry. However,
some of these compounds have limitations, such as formaldehyde release, toxicity, effluent generation, reduction in strength,
stiffening of fabric, shade change and liberation of toxic gases. New innovative routes to develop flame retardant textiles
like nanotechnology, plasma, and layer-by-layer techniques and intumescent flame retardant coating are explored by the
researchers. To achieve sustainable FR finishing, finishes based on natural resources are also explored. Hydrogel-based FR
finishing is an innovative area with a great prospect of exploration in flame retardant textiles. This paper reports a
comprehensive information on FR finishing of textiles. The advanced methods for producing flame retardant coatings,
including UV curing, microencapsulation, spray coatings, and sol-gel coating, are also reviewed.

Keywords: Flame retardant finishing, Hydrogel-based finishing, Intumescent flame retardant coating, Sustainable finishes

1 Introduction absolute protection to prevent such accidents. Fire

Among all the functional finishes for textile fighters, military as well as emergency personnel also
substrates, flame retardant (FR) finishing is the most need flame retardant textiles. Textile fibres, both
vital, as it is linked to human protection. When ignited natural and synthetic, are used in apparel, home
by a source, the textile material catches fire quickly, furnishing, hotels, hospitals, architecture, and
burns, and can cause hazards. If the same textile transportation (railways, aeroplanes). Natural fibres,
material is finished with efficient flame retardant, the like cotton, wool, silk, and flax, are prone to burning.
propagation of flame is stopped, and the fire gets The situation in the case of synthetic fibres is more
extinguished once the ignition source is removed. The complicated as they shrink, melt, and burn at a faster
limiting oxygen index (LOI), indicating the minimum rate when in contact with flame. Shrinking of the fibre
oxygen concentration in the oxygen-nitrogen mixture and dripping of the molten backbone of synthetic fibre
required to support candle-like burning, is an (polymer) can cause a high degree of skin burning. The
important indicator of flammability. Also, textiles lower LOI value of textile fibres makes flame retardant
with LOI of less than 21 can catch fire readily and finishing a requirement for most of them. Hence, it
burn in an ambient atmosphere. Textiles with LOI becomes an indispensable aspect of producing textiles
between 21 and 27 can also catch fire, but they burn finished with flame retardants1–4. The thermal transition
slowly in the ambient air. Textiles with LOI greater temperatures of different fibres and their LOI are
than 27 are generally considered flame retardant depicted in Table 1.
materials. Apart from LOI, the peak heat release and
burning rates are crucial for flame retardant textiles. 1.1 Mechanisms of Flame Retardant Finishing of Textile
Materials
The burning behaviour of textiles will also depend on
The mechanism for imparting flame retardancy to a
the type of textile structure directly related to the
textile material can be easily understood by first
availability of oxygen passing through the textile
studying the fibre combustion process in the presence
structure.
of the ignition source. Combustion is an exothermic
Fire accidents can occur anywhere at any time;
process which needs three components for burning,
hence, flame retardancy became essential for providing
i.e. heat, oxygen, and fuel. The combustion process is
—————— self-catalytic and proceeds until the heat, oxygen, and
a
Corresponding author. fuel are depleted. When a heat source is applied to
E-mail: [email protected] any textile material, its temperature rises, and the
476 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

Table 1 — Thermal transition temperatures and limiting oxygen index of different fibres
Fibre Glass transition Pyrolysis Melting Combustion LOI, % Ref.
temp. (Tg),°C temp. (Tp), °C temp. (Tm), °C temp. (Tc), °C
Cotton - 350 - 350 18-18.5 4-6
Viscose - 350 - 420 18.9 4
Wool - 245 - 600 23.6-25 4,7,8
Polyester 70-90 420-450 255 480 20-21 4,9
Nylon 6 47-50 431 215 460 20-21.5 4
Acrylic 100 250 >220 290 18.2 4
Polypropylene -20 469 165 550 18.6 4

Fig. 2 — Decomposition reaction of (A) calcium carbonate, (B)

aluminium trihydrate and (C) boric acid

prevent flame propagation. Examples of such an

approach are using calcium carbonate or aluminium
trihydrate coatings onto the textile substrate, as
Fig. 1 — Combustion cycle of a fibre2 depicted in Figs 2 (A) and (B). Such inorganic
materials do not have chemical bonding potential with
pyrolysis temperature (Tp) is reached. Formation of textile fibre. Hence, this finish lacks wash-durability.
various non-flammable gases, such as water vapour, Another approach could be, forming a glassy or
carbon dioxide, higher oxides of sulphur and nitrogen, foamy insulating layer onto the fibre surface at a
carbon char and tar (liquid condensates); and temperature below the pyrolysis temperature. A
flammable gases like hydrogen, carbon monoxide, glassy layer insulates the textiles and further prevents
and other oxidizable organic volatiles occursduring combustion. Boric acid and its various hydrated salts
pyrolysis. These flammable gases rapidly burn when work on this approach, as depicted in Fig. 2(C). When
in contact with oxygen, leading to heat energy heated, it produces a foamed glassy surface and
liberation. Thus, a further rise in temperature leads the releases water vapour.
fibre to reach its combustion temperature (Tc). The However, another approach involves altering the
generated heat energy accelerates the pyrolysis of pyrolysis temperature of the fibre. Due to this, the
polymer again, which consecutively generates more formation of non-flammable gases occurs, which
flammable gases, leading to intense combustion1,2. prevents the fibre from further burning. The dilution
The illustration of the combustion cycle of fibre is of oxygen and flammable gases is another approach
depicted in Fig. 1. for reducing the flammability of the textile substrate.
The various mechanisms for preparing an effective Either the replacement or dilution of the surrounding
flame retardant textile material are further discussed. oxygen and flammable gases can be done by using
One such approach could be absorbing the heat inert and non-flammable gases to either diminish or
from the strong endothermic reaction caused by fire- end the combustion process.
retardant material. This will prevent the attainment of Another approach involves stopping the
pyrolysis temperature, suppress the combustion, and combustion via interference with the help of free
reduce the burning surface temperature. It will also radical reactions, which further prevents the
limit the production of combustible gases, which continuous burning1,2. Figure 3 indicates the
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 477

countries, some of these toxic formulations are

banned.Various flame retardants available for textile
finishing are discussed in further sections.

2 Traditional Flame Retardants and Related Issues

2.1 Inorganic Flame Retardants
Inorganic flame retardants include compounds like
aluminium hydroxide, aluminium trioxide, and
magnesium hydroxide. When heated by a source,
Fig. 3 — Competing free radical reactions during combustion of aluminium hydroxide releases water vapour, which
halogen-containing material cools the textile material to a temperature below that,
which is required for sustaining the combustion
mechanism of halogen-based compounds through the process. Even the water vapour liberated helps in the
quenching of free radicals to provide the flame dilution of gases, and the oxide layer formed on the
retardancy totextiles. textile material helps to form an insulating protective
Intumescence is another approach that could be char layer12. Generally, aluminium hydroxide is
used to suppress the flammability of textiles. For required in large amounts to impart flame
impartingintumescentflame retardant behaviour, it retardancy13. These flame retardants can be applied to
must consist of three main components, namelyan textiles using exhaust and padding methods. The
acid source (phosphoric acid-based source), a mechanical properties of textiles will change by using
carbon/char source, and a blowing agent (nitrogen- a higher amount of flame retardants.
containing systems). On exposure to a flame source,
the intumescent material degrades and forms an 2.2 Halogen-based Flame Retardants
insulating char that can entrap the gaseous species and Halogen-based flame retardants are generally based
prevent the burning10. A lesser amount of any of the on chlorine and bromine chemistry. These compounds
threecomponents will not give the desired outcomes. work on the radical chain mechanism, which occurs in
the gas phase during combustion. Compounds like
1.2 Durability of Flame-Retardants on Textiles
decabromodiphenyl or pentabromodiphenyl ethers, and
One major issue with the flame retardant finishes is
polychlorinated biphenyls are effective, but these are
the limited durability against washing treatments.
banned due to their toxicity. These compounds are
Alkaline washing treatments using anionic surfactants
proven to be persistent and bio-accumulative. Also, the
can also affect durability because such surfactants can
finish is not durable and can be removed easily by
make complexes with cationic flame retardants. Even
washing. Chlorine and bromine compounds, along with
if the textile is exposed to sunlight and weathering
antimony, have also shown synergistic results in flame
conditions, durability gets hampered. The combined
retardancy, but due to adverse environmental impacts,
action of sunlight and laundering can significantly
halogen-based compounds are not recommended1,12,14,15.
lower the durability11. The effectiveness of durability
can be improved using fibre-reactive flame retardants. 2.3 Phosphorus-based Flame Retardants
As per the retention of flame-retardancy after Halogen-based formulations show negative
repeated launderings, flame retardant textiles can be environmental impacts and are replaced by
classified as non-durable (washed off immediately phosphorus-based flame retardants. Under the effect
after being laundered but are unaffected by dry of flame, these phosphorus compounds form
cleaning), semi-durable (unaffected by water soaking phosphoric acid, which acts in a condensed phase by
and a few wash cycles), and durable (can withstand forming char. Phosphorus-based flame retardants are
50 -100 washcycles)10. divided into inorganic, organic, and halogen-
Halogen, phosphorus, and nitrogen-based containing categories. These compounds are easy to
compounds are quite effective. Still,some havevarious apply and could be used to finish a wide range of
associated issues like formaldehyde release, toxicity, textile fibres. Ammonium polyphosphate and red
effluent generation, reduction in tear and tensile phosphorus are the flame retardants with the least
strength, stiffening, shade change, and the liberation issues, but certain health effects could not be ignored.
of toxic and corrosive gases. Even in certain Phosphorus-based flame retardants are found to be
478 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

less toxic as compared to the halogen-based ones12,14. melting temperature is lowered by borax, releasing
The decomposition and combustion behaviour of water vapour. A thick layer of boron trioxide is
fibres are changed by phosphorus-based compounds, formed, which insulates and prevents the textile
which promotes char formation. Some phosphorus substrate from burning. As no chemical bond is
compounds release free radicals, which react with formed with the textiles, the finished textile loses its
H and OH radicals to prevent further decomposition. efficacy after the first wash1. Cross-linkers can
The mechanism of flame retardation is related to the provide a strong bonding between textiles and flame
interaction of flame retardant with textiles, the retardants. Most of the available traditional flame
chemical structure of flame retardant, and the textile retardants are not reported to be eco-friendly and
substrate. possess various drawbacks, such as:
During the application of finish and usage of  Reduction in tear and tensile strengths and an
finished textile, small molecules of organophosphorus increase in the fabric's stiffening, especially in
FR agents are released into the water bodies. cases where the acidic catalyst is used along with
These compounds are also environment-persistent, the flame retardant formulations.
bio-accumulative, and possess various ecological  High drying and curing temperatures are required
risks16. Further, formaldehyde is released from the to apply such commercial and traditional flame-
phosphorus-containing compounds having N- retardants, which makes the process quite a time
methylol groups3. These organophosphorus FR agents and energy consuming, consequently increasing
are also responsible for eutrophication and pollution17. the cost.
2.4 Phosphorus and Nitrogen-based Flame Retardants  Bromine and chlorine-based halogenated flame
Phosphorus and nitrogen showa synergistic effect retardants are toxic, hazardous, and bio-
for flame retardancy on textile substrates.At higher accumulative.
temperatures, phosphorus-containing flame retardants  Certain formulations are even sensitive to various
form phosphoric acid that crosslinks with the dyestuffs.
hydroxyl group of cotton. Nitrogen acts in synergism  Release of formaldehyde from the flame retardant
with phosphorus-containing flame retardants and treated fabrics, which contains methylolated
increases efficiency. These compounds produce more cellulose cross linking groups. Formaldehyde
char compared to that obtained with the halogen- release is reported as carcinogenic and poses
based ones. Pyrovatex (N-methylol phosphono health hazards to industrial workers and to the
propionamide derivatives) and Proban (hydroxy environment.
methylphosphonium salts) are used on cellulosic  The complex curing process can cause issues
fabrics. Tetrakis (hydroxymethyl) phosphonium related to health and well-being.
chloride (THPC) and urea formulations can affect dye  Discharge of harmful compounds into the effluent
classes like direct, reactive, and acid dyes. In the case after finishing of the fabric could affect the
of Pyrovatex, after the first wash of the finished environment1,20.
textile, 50% of the flame retardant gets removed1,18.
Proban and Pyrovatex require adverse acidic 3 Flame Retardancy Using Nanotechnology
conditions and higher add-on (%)for their application on Nanotechnology-based finishes are efficient
the textile substrate to impart effective flame retardancy. alternatives to traditional flame retardants.
These flame retardants are applied through padding, Nanotechnology deals with the phenomenon that
drying and curing; however, such treatments could also occurs at atomic and molecular levels using a 1-100
impartstiffness to the fabric. This might cause a nm length scale in any dimension, which can be used
reduction in its tensile strength. Besides, these to control or manipulate matter at the atomic scale21.
treatments are expensive, non-eco-friendly, and require a 3.1 Montmorillonite
high curing temperature19. Nitrogen-containing fibres Montmorillonite, a nano clay particle, is a
such as wool and silk can make a synergistic chemically hydrated sodium calcium aluminium
combination with phosphorus-based flame retardants. magnesium silicate hydroxide, known for its
2.5 Borax and Boric Acid-Based Flame Retardants application in the coating to impart flame retardancy
Borax and boric acid formulations are also known to cotton and polyester fabrics. However, the exact
to impartflame-retardancy totextiles. Boric acid’s mechanism of action is not known. It is assumed that
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 479

the nano clay gets deposited on the fabric surface and and bio-based compounds could be better than
forms an oxygen barrier, thus retarding the burning traditional flame retardant chemicals. Its
process and forming a char layer. Nano clayalone is disadvantages, like hampering the elastic properties of
insufficient to impart flame retardancy and, hence, the treated PA66 fabric due to the cross-linking are
can be combined with conventional compounds. As observed. Since there is no improvement in the anti-
nano clays are biodegradable and obtained from dripping properties of treated PA66 fabric, further
purely natural sources, they are regarded as eco- optimisation is required23.
friendly21. Various approaches, such as incorporating
nano clay particles during the manufacturing of fibres 3.4 TiO2 Nanoparticles along with Proteins
and coating of nano clay particles to textiles, can be Combining TiO2and protein systems applied using
utilised. The first one can give an efficient wash- a dip-pad-dry-cure method impart flame retardancy to
durable effect due to the entrapment of particles the cotton fabric. It is observed that the nanoparticles
inside the fibre. and protein-based system decrease the burning rate
with an increase in burning timeinthe horizontal
3.2 Zinc Oxide Nanoparticles flammability test24.
Zinc oxide nanoparticles were also utilised in the Nanoparticles show promising flame retardant
flame retardant coating of cellulosic textiles. Zinc outcomes. However, toxicity associated with
oxide nanoparticles were applied to various substrates nanoparticles is a significant concern, preventing the
(100% cotton and 65/35% cotton/polyester blend) commercialization of such molecules.
using polycarboxylic acids, such as butane
tetracarboxylic acid (BTCA), succinic acid,and 4 Flame Retardancy Using Layer-by-Layer Assembly
sodium hypophosphite (SHP) via the pad-dry-cure Technique
method. The combination of malic acid (MA), SHP, Layer-by-layer (LbL) technique is hailedas an
and hydroxyalkyl functional organophosphorus evolution of nanoparticle adsorption process. Based on
compound, along with BTCA,is also reported for electrostatic interactions, step-by-step films are built.
imparting flame retardancy. The finished cotton fabric The LbL was first described in 1966 but re-discovered
shows some yellowness. Additionally, zinc oxide several years later25. It is a water-based method to form
works as a catalyst to increase the char formation multilayer films, by alternate deposition of positively
when used along with polycarboxylic acid and SHP. and negatively charged polyelectrolyte onto the textile
With the use of SHP, phosphorus is deposited on the fabric. Flame retardancy can be imparted using the LbL
fabric, which results in a higher quantity of char, there assembly technique with hybrid organic-inorganic, all-
by decreasing the flammability of the treated fabric. inorganic, and all-polymer in tumescent systems26. Each
To reduce the flammability of fabric, BTCA showed positive and negative pair of films deposited onto the
better results than succinic acid22. fabric is termed abilayer (BL)27.
3.3 TiO2 and SiO2 Nanoparticles along with Chitosan and 4.1 Cationic Chitosan along with Anionic Ammonium
Phytic Acid Polyphosphate
Applying TiO2 and SiO2 nanoparticles along with Researchers also utilised cationic chitosan and
chitosan and phytic acidshow reduced flammability of anionic ammonium polyphosphateto prepare cotton
treated polyamide 66 (PA66) fabric. When phytic acid fabric with an excellent intumescent flame-retardancy
and TiO2/SiO2 nanoparticles are used together, the using the LbL technique. Chitosan works as a carbon
LOI (24.5) of fabric and char yield increase. Further, donor and blowing agent, whereas ammonium
the application of chitosan in combination with phytic polyphosphate is an acid donor. After evaluating
acid and TiO2/SiO2 nanoparticles as the active coated fabric, increased residual char production
components and BTCA as a cross-linker on PA66 decreased peak heat release rate, and total heat release
fabric through pad-dry-cure technique shows an rate due to accelerated charring and inhibition of
intumescent and thermal shielding effect, which volatile gases is observed. The coating with 20 BL
results in the reduction in peak heat release rate could lead to effective fire retardancy with the treated
(-25%). Along with flame retardancy, the fabric's self-extinguishing behaviour. However, an
hydrophilicity and tensile strength of the fabric increase in the number of bilayers on the fabric results
arealso enhanced. Hence, combining nanoparticles in a stiff handle of treated fabric26.
480 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

4.2 Cationic Chitosan and Anionic Phytic Acid with less than 5% weight deposition on cotton fabric,
A combination of cationic chitosan and anionic the self-extinction of flame is observed. A significant
phytic acid is considered as a green and completely reduction in the total heat release rate (-40%) is also
bio-renewable source for imparting flame retardancy observed in cone calorimetry29.
to the cotton fabric using the LbL assembly technique.
Phytic acid is a source of phosphorus, while chitosan 4.5 Potassium Alginate (PA) and Polyhexamethylene
consists of nitrogen. When both these components are Guanidine Phosphate (PHMGP)
combined, it results in a renewable intumescent The environment-friendly antimicrobial PHMGP is
coating on cotton fabric. The thinnest films combined with potassium alginate, a green polymeric
(30 BL~10nm thick) are obtained at a pH 4. It is material extracted from seaweed, for coating cotton
observed that coated fabric completely extinguishes fabric using the LbL technique to impart antimicrobial
the flame, reducing the peak heat release rate (-60%) and flame retardant properties. The coated fabric
and total heat release rate (-76%). It is believed that shows more char residue as compared to the uncoated
such behaviour is ascribed to the presence of high one. Vertical flammability results for the coated fabric
phosphorus content, which enhances the intumescent have shown the elimination of the after-glow
behaviour of the coated fabric27. phenomenon at 2s after extinguishing. Also, there is a
reduction in the peak heat release rate and the total
4.3 DNA and Chitosan heat release rate of the coated cotton fabric. The peak
DNA and chitosan are also reported in the literature heat release rate decreases with increased BL for the
for their application viathe LbL technique on the coated cotton fabric. The intumescent coating is
cotton fabric as a green coating for imparting fire formed, which shows excellent flame retardant and
resistance. Due to its chemical structure, DNA antimicrobial properties30.
imparts intumescence to the cotton fabric. DNA is a The main issue encountered in the LbL assembly
precursor of phosphoric acid the deoxyribose acts as a technique for obtaining flame retardancy is the
char source, and the bases containing nitrogen might requirement of more bilayers to achievea significant
release ammonia. When combined with chitosan, effect. However, applying morebilayers might result
DNA helps in the easy formation of a thermally stable in a stiff handle of treated fabric26. Thus, higher
char, making this system highly efficient. After 5 BL number of bilayers should be avoided.
deposition of DNA and chitosan, smooth coatings are
observed as compared to the untreated cotton fabric. 5 Plasma-Assisted Flame Retardant Finishing of Textiles
20 BL assemblies of DNA and chitosan impartes the Permanent fireproofing on fabric such as cotton is a
self-extinguishing behaviour of cotton fabric, challenging aspect. Moreover, the coating formed
increasesthe LOI (up to 24), and reducesthe heat must be resistant to washing and remain attached to
release rate by 40%. Although the DNA used is the fabric's surface. Hence, experiments are carried
expensive as compared to other chemicals, the out to form durable flame retardant coatings using
required degree of purity for the flame retardant plasma technology31. This section mainly discusses
application is much lower than that needed for the use of plasma to fixor cureflame retardant
biological use and could be compensated; hence, it chemicals on the textile materials.
could lead to a reduction in cost28. PAN fabric is treated using argon plasma, with four
acrylate monomers (containing phosphorus) such as
4.4 Cationic Starch along with Polyphosphoric Acid dimethyl(acryloyloxymethyl)phosphate (DMAMP),
Cationic starch, along with polyphosphoric acid, diethyl(acryloyloxyethyl)phosphate (DEAEP),
are coated on the cotton fabric using the LbL diethyl(acryloyloxymethyl)phosphate (DEAMP), and
technique. Starch is also used as a sustainable, bio- diethy-2-(methacryloyloxyethyl)phosphate (DEMEP).
based efficient coating, protecting the cotton from Also, new phosphoramidate monomers (such as diethyl
catching fire and causing the associated hazards. (acryloyloxyethyl) phosphoramidate (DEAEPN) and
Starch, upon heating,can form a thermally stable char acryloyloxy-1,3-bis(diethylphosphoramidate) propan
layer. The dehydration ability of polyphosphoric acid (BisDEAEPN))are synthesised, and their plasma-
has further improved the effect. It is also observed induced graft polymerisation on the cotton fabric is
that after the coating application, the char-forming reported. It is detected that using DEAEPN, the LOI
ability is further enhanced. After applying only 2 BL value of cotton fabric reached 28.5, while treatment with
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 481

BisDEAEPN enhanced the LOI value of cotton to 29.5. environmental impacts but also help in reducing the
This could be further explained by the presence of carbon footprint. In the last 5-10 years, studies have
phosphoramide monomers, consisting of nitrogen, essentially been carried out to obtain eco-friendly
which synergistically enhanced the performance of biomolecules, either extracted from plants (grains and
phosphorus-based flame retardants. Even after sap-based) or animal (polysaccharides or protein-
laundering, an LOI of 25 is maintained for the fabric based) natural sources for producing flame retardant
treated with acrylate phosphoramide monomers and textile material. Instead of throwing it into the
DEAEP31. landfill, the agro-food industry waste could be utilized
Atmospheric pressure dielectric barrier discharge as a flame retardant finish for textiles. Even the
plasma has also been experimented with by process of application of biomolecules on textiles is
researchers. The plasma-treated fabric is further simple, and the application can be done using already
treated with flame retardants through the conventional existing systems of the textile industry. Also,
pad-dry-cure method. It is reported that to achieve biomolecules are dissolved or suspended in lower
LOI value of 25 using plasma, the time and concentrations in an aqueous medium such that no
temperature for curing are 90s and 160°C, as volatile organic carbon (VOC) species are generated.
compared to 114s and 180°C respectively, achieved in Most plant extracts and waste animal products
the absence of plasma treatment. Though the contain phosphorus, nitrogen, other inorganic
reductions in time and curing temperature are compounds, and metal oxides, which could be utilised
achieved, a substantial loss in the treated fabric's to impart flame retardancy to cellulosic, protein-based,
mechanical strength is seen. It is also stated that and lignocellulosic textile materials34–36.
plasma itself is responsible for reducing the 6.1 Animal-based Natural Resources for Flame Retardant
mechanical strength of the fabric. It is suggested that Finishing of Textiles
the time for plasma pre-treatment must be further Various animal-based natural resources are already
reduced so that the chemical bond between cotton and reported in the literature for imparting flame
treatment chemical could be formed with the retention retardancy to the textile substrate. The animal-based
of mechanical strength of fabric32. natural resources with potential applications in flame
Researchers also reported atmospheric pressure retardant finishing of textiles are depicted in Fig. 4.
plasma as a pre-treatment on the cotton fabric to
6.1.1 Chitosan
enhance post-finishing (flame retardant properties).
Chitosan, an amino polysaccharide obtained via
Plasma pre-treatment is reported to improve the flame
alkaline deacetylation of chitin, is an eco-friendly
retardancy of cotton fabric treated with an organic
phosphoric acid (fire retardant) with melamine resin
(cross-linker), phosphoric acid (catalyst), and zinc
oxide(co-catalyst).The treated cotton sample with the
prepared formulation showed a reduction in
mechanical properties, which were further
compensated by the plasma pre-treatment33.
The technology of plasma is known as waterless and
eco-friendly, but still, it is a costlier process for
producing flame retardant textiles32. Poor result
reproducibility is another undesirable aspect associated
with plasma technology.
6 Natural Resources-based Sustainable Green
Flame Retardants for Textile Finishing
In an era where sustainability and growing
environmental awareness are evident, producing eco-
friendly flame retardant fabrics has become essential.
These environment-friendly flame retardant finishes
will not only protect from major human health Fig. 4 — Animal-based natural resources for flame retardant
hazards, associated toxic effects, and negative finishing of textiles
482 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

natural source to impart flame retardancy to cotton The protective coating absorbed heat, formed char
fabric. Researchers37 dissolved chitosan in the citric and released inert gases38.
acid solution, added it to a phosphorylation bath
consisting of butane tetracarboxylic acid (BTCA), 6.1.3 Whey Proteins
diammonium hydrogen phosphate (DAHP), and Whey proteins, the by-product of cheese, could
sodium hypophosphite (SHP), and then applied it to also be used to form coatings onto the cotton fabric,
cotton fabric. Chitosan, when added, acted as a which can potentially impart flame retardancy. Whey
nitrogen source in synergy with phosphorus during protein isolate (WPI) shows better mechanical and
the phosphorylation process. It is also reported that excellent oxygen barrier properties despitehaving
when the chitosan concentration is increased from 1% water adsorption capabilities. It forms transparent,
to 2%, enhancement in flame retardancyis observed. colourless, odourless, and flexible films onto the
Increasing the concentration above 2% showed a cotton fabrics. In some cases, plasticizerscan be
limited impact on the treated fabric's thermal applied within the protein mixture to form films and
degradation. DAHP (concentration varying from 0% decrease the film brittleness. These films reduce the
to 10%) is added to the bath to obtain durability intermolecular forces between adjacent protein
against washing. The optimum concentration of chains, thereby imparting more extensibility and
chemicals for reduced flame retardancy is 1% flexibility. Researchers utilized whey proteins (folded
chitosan, 10% DAHP, 4% BTCA, and 6% SHP37. and unfolded) and proved them to be the potential
sources for enhancing flame retardancyin cotton
6.1.2 Deoxyribonucleic Acid (DNA) fabric. An increased burning time and reduced
DNA obtained from the herring sperm isalso burning rate are observed for the treated cotton
utilised to impart enhanced flame retardant properties fabric39.
and thermal stability to the cotton fabric. DNA is
considered as an intumescent flame retardant, as it 6.1.4 Caseins and Hydrophobins
comprises all three components needed to show Caseins and hydrophobins are other finishes for
intumescent behaviour. It contains phosphate groups, reducing the flammability of cotton fabric. Caseins
which could form phosphoric acid; the deoxyribose consist of phosphorus-rich proteins, while
unit, which acts as a carbon source and a blowing hydrophobins consist of sulphur-rich proteins. The
agent (which, upon heating, form char and release proteins obtained from animal or microbial sources
water); and the nitrogen-containing bases (adenine A, can also be utilised for imparting flame retardancy to
cytosine C, guanine G, and thymine T), which might cotton fabric. Casein is a milk protein (80%) obtained
release ammonia. It is observed during the during skimmed milk production, while hydrophobins
flammability testing in a horizontal configuration that are obtained from filamentous fungi. These proteins
the the fabric did not burn even after applying flame induce dehydration of cellulose in place of
for 3 s. The LOI value of 28 is reported for DNA- depolymerization, thereby producing a thermally
treated fabricas compared to LOI of 18 for the stable char. Also, it is reported that the fabrics coated
untreated one. However, the main issues with DNA with caseins and hydrophobins show higher burning
include its high cost and poor durability in washing5. time (40% higher), reduce the total burning rate
In another experiment, DNA in various (lower by 35%), and form a consistent residue40.
concentrations (5, 10, 19 wt %) is coated on the Caseins (from bovine milk), due to their high
cotton fabric, considering percentage weight increase phosphorus content, are also used to improve the
of fabric sample after finishing relative to the original flame retardancy and thermal stability of polyester
weight of the fabric sample (wt.%). It is detected that and polyester-cotton fabrics via impregnation
10 wt.% DNA is the least amount that must be applied methods. This biomacromolecule could produce char
to the cotton fabric to achieve self-extinction when and inhibit the formation of volatile species. The
subjected to a methane flame. Also, in the case of thermal stability of the casein-treated fabric increases
19wt. % DNA, the treated fabric can resist the along with resistance to an irradiative flux, in the case
irradiative heat flux of 35 kW/m2. The DNA-treated of both nitrogen and air atmosphere. A reduction in
cotton fabric did not burn in cone calorimeter testing. the burning rate (-70%) and an increase in LOI value
Due to the protective coating done by DNA, the (21 from 26) are observed in the case of polyester
treated cotton fabric ispyrolyzed instead of burning. fabric. The burning rate is slowed down (-40%), and
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 483

even resistance to irradiative flux, is reported for the retardancy to the textile substrate are depicted in
polyester-cotton blend treated with caseins. However, Fig. 5.
the issue of melt dripping for the polyester fabric still
needs to be solved9. 6.2.1 Spinach Leaves Juice
The application of casein phosphopeptide (CPP) Spinach leaves juice, a vegetable extract, is used to
along with ferrous and titanium sulphates is also reduce cotton fabric’s flammability. Flame retardancy
reported in preparing durable flame retardant silk fabric. in the spinach juice-treated textile can be ascribed to
The silk fabric treated with 10 g/L CPP and mordanting proteinous nitrogen, metal salts, and silicates. The
with ferrous and titanium sulphates show LOI values of extracted juice is applied to the bleached and
27.8 and 28 respectively, along with smoke-suppressant mercerized cotton fabric in alkaline conditions.
effects. A residual char length of less than 15 cm is Compared to the untreated fabric, the treated fabric
observed even after 20 wash cycles. A condensed phase shows good flame retardancy. After applying spinach
mechanism is proposed in which the complex of CPP juice extract, the LOI value of the treated cotton
and metal ions work. The good charring ability of fabric is increased. The total burning time also
treated fabric and the enhanced thermal stability, even at increased, which can help to provide extra time for
high temperatures, are the factors responsible for escaping the fire hazard zone to extinguish the fire.
increasing flame retardancy. Bright yellow colour with The total heat generation for the treated fabric is
good wash and rub fastness properties is also imparted41. further reduced. Another advantage in terms of good
weathering fastness propertiesis claimed. The natural
6.1.5 Chicken-Feather Protein green colour is imparted to textile, which makes it
Chicken-feather protein, another eco-friendly, suitable for application in colouration and imparting
protein-based, nitrogen-containing flame retardant, flame retardant finish for home furnishing products.
isutilised to treat cotton fabric. Chicken feather protein, In alkaline conditions, it is observed that without any
along with nitrogen and phosphorus-containing dilution for the spinach juice extract, i.e. (1:0) is the
monomers (melamine and sodium pyrophosphate), and a best for imparting flame retardancy43.
crosslinker (glyoxal) are used. The P-N based chicken-
feather protein FR, along with borax and boric acid, are 6.2.2 Banana Pseudostem Sap (BPS)
applied to the woven cotton fabric. An enhanced flame BPS, a green plant extract from a renewable
retardancy along with thermal stability of the treated source, also showed promising results in imparting
fabric, due to the formation of a compact and flame retardant properties to cellulosic fabrics. The
homogenous in tumescent char layer, is reported. LOI sap extracted from the plant is made alkaline and then
values obtained are also higher than the control fabric. It applied on the pre-mordanted, bleached, and
is also stated that chicken feather protein acted mercerized cotton fabric. The non-diluted BPS
synergistically with borax and boric acid42. application on cotton textiles under alkaline
Results in terms of LOI, add-on percentage on cotton conditions showed the best results, as the increased
fabric, burning rate, burning time, and residue of a few LOI values were obtained. In the vertical
natural-based animal resources already discussed in the flammability test, the flame is observed for the first
previous paragraphs are depicted in Table 2. 10 s, and then it got extinguished. In the case of the
6.2 Plant-based Natural Resources for Flame Retardant horizontal flammability test, no flame is observed, but
Finishing of Textiles burning with afterglow is seen. The flame retardant
The various plant-based natural resources properties shown by the BPS-treated cotton fabric are
reported in the literature for imparting flame ascribed to the presence of phosphate, nitrogen, metal
Table 2 — Summary of natural animal-based resources for FR finishing of cotton
Natural animal-based resource LOI, % Add-on, % Burning rate, mm/s Burning time, s Residue, % Ref.

Control cotton fabric 18 - 1.5 78 - 39

DNA 28 19 - - - 5
Whey protein (unfolded) - 20 1.1 133 5 39
Whey protein (folded) - 25 1 126 30 39
Caseins - 20 1 100 34 40
Hydrophobins - 20 1.1 104 19 40
484 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

Fig. 5 — Plant-based natural resources for flame retardant finishing of textiles

salts (potassium chloride and sodium chloride), and grains, beans, and oilseeds. Phytic acid comprises
inorganic materials. These compounds assisted in the 28% phosphorus (based on its molecular weight),
formation of char and non-flammable gases during the which can be used as a phosphorus source in the
burning of treated cotton. Also, BPS showed inherent flame retardant finishing of textiles. Researchers
dyeing properties as a natural khaki colour is applied PA on wool fabric using the exhaustion
produced after the application on cotton fabric, which method. A good flame retardancy is observed for
is stable to sunlight exposure. The simple and cost- treated wool. Due to its high char-forming ability, it
effective process can be used to provide both works through a condensed phase mechanism.
colouration and functionalization44. However, PA has shown slight adverse effects on the
An eco-friendly agricultural waste product is also strength and whiteness of the treated wool fabric.
used on proteinous wool fabric to impart flame Also, the washing resistance of treated wool fabric
retardancy. An acid dye (CI Acid Blue 25) dyeswool could be better and needs to be improved8.
fabric using water and BPS asthe medium. Dyeing, In another study, it is reported that PA can enhance
with the help of BPS at a pH of 5.5, showed more the flame retardancy of silk/wool blend fabric. The PA-
colour strength, colour exhaustion, and thermal treated blend exhibited inferior FR properties compared
stability than untreated wool fabric. The treated wool to the conventional agents (K2TiF6 and K2ZrF6).
fabric exhibits self-extinguishing behaviour at a However, the treated blend showed better FR properties
specific char length with increased LOI values. It is after washing. Compared to the conventional systems,
also stated that instead of water, BPS could be used as PA acted as the best smoke suppressant, reduced the
a dyeing medium7. heat release capacity, and gave the best catalytic char-
forming effect. However, the whiteness of the blend is
6.2.3 Phytic Acid (PA) reduced due to the action of PA45.
PA, a bio-based, naturally occurring compound,
has also shown promising results for imparting flame 6.2.4 Green Coconut Shell Extract (CSE)
retardant properties to wool fabric. It is identified as Green coconut (Cocos nucifera Linn.) shell extract,
inositol hexakisphosphate acid or phytate in salt form a waste bio-resource, is also used to impart flame
and is considered an eco-friendly biomolecule, as it retardant properties to textiles. Green coconut
can be obtained from plant tissues such as cereal mesocarp is cut into pieces, and sap is extracted.
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 485

Researchers applied CSE on the cotton fabric under cheaper, and more reliable than that of the purified
different pH conditions, i.e. acidic, alkaline, and fish DNA. For both purified DNA and brewer's yeast
neutral. The dimensions of the CSE obtained were in nucleic acid, the add-on values (8 wt. %) on the fabric
nanoscale and were applied by using the exhaustion were equal. Self-extinguishing and similar behaviour
method. After the application of CSE on the fabric in are observed for both purified DNA and the spent
alkaline conditions, it is observed that the LOI brewer’s yeast. However, the nucleic acids obtained
increased by 72.2%. This increase could be attributed from vegetable scraps were not as effective, which
to the presence of different inorganic and organic might be due to the lower final dry add-on values
compounds; the formation of char layers at a lower (about 5 wt. %). Hence, the nucleic acid obtained
temperature, which act as a protective barrier against from agro-food waste is found to be a good alternative
flame and heat; and reduced volatilization, which to expensive purified DNA49.
further reduced the formation of combustible gases.
CSE also formed a coating layer onto the fabric, 6.2.6 Tannic Acid
which acted as a fire barrier. A condensed phase in Tannic acid, a natural polyphenolic compound
tumescent mechanism is proposed. A natural brown along with sodium ions, is also reported to produce an
colour is obtained, which could change to red with intumescent flame retardant cotton fabric. A low
increased pH. The treated fabric even exhibited thermal conductivity, along with low flammability, is
antibacterial properties against Gram-positive and exhibited by the treated cotton fabric. It is reported
Gram-negative bacteria46. that tannic acid alone is sufficient to change the
CSE is also applied on the jute fabric. The extract thermal pattern of pyrolysis and combustion of cotton,
is acidic; and hence, it is made alkaline and neutral along with an increment in char length; however, the
before applying to the jute fabric. Good flame LOI value is not enhanced. Hence, alow concentration
retardant properties and an increase in thermal of sodium hydroxide is added to enhance flame
stability are observed, along with an increase in LOI retardancy. Sodium ions led to increased adsorption
by 48% under alkaline conditions and 81% in of tannic acid on the cotton fabric, and catalyzed the
concentrated conditions. The reduced flammability is decarboxylation of tannic acid, and dehydration of
ascribed to the presence of phosphate compounds and cellulose. The intumescent char layer obtained
inorganic metals, which are responsible for producing resulted in a reduction of heat release capacity by
more char and non-flammable gases. Apart from 82% and increased LOI to 30.250.
flame retardancy, the jute fabric also showed natural Condensed tannins obtained from Dioscorea
colour, UV protection, and antibacterial properties. cirrhosa (DC) tuber, a natural plant source, also
Comfort and strength are retained even after the impart flame retardant properties to silk fabric. The
application of CSE47. aromatic structure of tannins is the suitable reason for
CSE is also utilised to impart multifunctional its application in thermal insulations and FR fabrics.
properties, such as flame retardancy, UV protection, Eco-friendly, nontoxic condensed tannins, when
and colouration on the proteinous wool fabric. The applied in a weakly acidic condition using the
concentrated CSE is applied to the wool fabric at a pH impregnation method, provided excellent and durable
of 4.5. CSE-treated wool fabric shows more flame retardant properties to silk fabric. It had been
exhaustion, good colour strength, and enhancement in reported that condensed tannins on silk fabric worked
thermal stability than the treated wool with synthetic through a condensed phase mechanism. Also, 300 g/L
acid dyes. An increment in the LOI value of the DC extract gave the highest LOI (28.1), while with
treated wool fabric is observed along with the fabric's the application of 37.5 g/L DC extract, good flame
self-extinguishing behaviour. The reduced retardancy is attained, as represented by the LOI value
flammability is ascribed to the presence of sulphate, of 27.2.A shorter char length is observed for the
phosphate, metal salts, silicates, etc.48. treated silk fabric compared to the untreated silk
fabric. Apart from flame retardancy, good antioxidant,
6.2.5 Nucleic Acid antibacterial, and UV protection properties are
Nucleic acidextracted from spent brewer’s yeast, imparted to the silk fabric. It is also reported that the
and vegetable scraps (agro-industrial biological treated fabric exhibits good durability to repeated
wastes)is also reported to impart flame retardancy to washing. When treated with DC extract, the silk
cotton fabric. This green extraction method is simpler, fabric gives a reddish-brown appearance, which could
486 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

be used as a natural dye source. With an increase in knitted fabric with excellent wash fastness
DC extract concentration, the treated silk fabric's properties53.
colour depth is found to be increased. This negatively In yet another study, pomegranate rind extract is
impacted the colour appearance of silk fabric, as also used to reduce the flammability of the
white FR silk fabric could not be produced using lignocellulosic jute fabric. An increase in LOI value
condensed tannins51. for the treated fabric to 38 is reported. A self-
Two coloured silk fabrics (Gambiered extinguishing behaviour for char length of 60 mm
Gauangdong silk) with shiny black on the face side isalso reported by researchers54.
and reddish-brown on the backside are produced
using condensed DC extract. A coating with 6.2.8 Tea Stem Waste
condensed DC extract followed by mordanting with A tea stem waste extracted after tea processing
iron salt consisting of mud is done to obtain flame could also be used forsimultaneous colouration and
retardancy. The coating formed char during flame retardancy to the silk fabric. The extract is
combustion,thus enhancing the flame retardant obtained in alkaline conditions. During the alkaline
properties of the treated silk fabric. Multifunctional extraction, the oxidative polymerization of
properties such as waterproof, flame retardancy, polyphenols led to the development of
antioxidant, and antibacterial properties are imparted macromolecular polyphenols responsible for
to the treated silk fabric52. imparting flame retardant properties to the silk fabric.
Tannic acid TA (hydrolyzable tannin form), The highest uptake by silk fabric is reported at a pH
naturally occurring polyphenols found in plants in the of 3 and a temperature of 30°C. The dyed silk showed
presence of ferrous ion mordant, also imparted good wash fastness properties; however, the
durable green antibacterial and flame retardant perspiration and wet rubfastness properties were poor.
properties to the silk fabric. It is reported that tannic Researchers further performed post-mordanting with
acid (20 wt. %) and 2 g/L ferrous sulphate are used in metal salts to improve the poor fastness properties.
combination with silk fabric to increase LOI value The treated silk fabric also exhibited good flame
from 23.6 to 27.5, an increase in antibacterial activity retardant, antibacterial, and antioxidant properties.
from 22% to 95%, and a decrease in damaged length. After post-mordanting, the flame retardancy is further
The treated silk fabric showed enhanced thermal enhanced, but a negative impact is observed on
stability in both nitrogen and air and retained its antibacterial and antioxidant properties. The improved
properties even after 20 washes. The ternary TA- flame retardant properties are ascribed to the
ferrous ion-silk complex works through a condensed increased charring behaviour of silk fabric after the
phase mechanism and is responsible for the excellent application of tea stem waste extract55.
wash durability of the functional properties of the
treated silk fabric. Enhanced flame retardancy 6.2.9 Bio-based Flavonoids Combined with Metal Salts
obtained could be explained by the charring layer Bio-based flavonoids, combined with metal salts,
formed onto the treated fabric17. are also known to impart flame-resistant properties.
Three kinds of bio-based flavonoids, namely
6.2.7 Pomegranate Peel Extract baicalin, quercetin, and rutin, are applied onto the
Pomegranate peel extract has also been reported to silk fabric using post-mordanting with metal salts.
impart flame retardancy to the cotton knitted fabric. In The smoke suppression, thermal behaviour, and
an experiment, zinc sulphate is used as a mordant for charred structures of silk fabric are studied. The
dyeing with pomegranate peel extract. The flame treatment of flavonoids followed by metal salt onto
retardant activity of the fabric treated with the silk fabricled to a good char formation, increased
pomegranate extract is stated due to nitrogen, LOI, flame suppression, and enhanced flame-
potassium, chlorine, and certain traces of other resistant properties. A good flame retardant,
elements, along with aromatic phenolic rings. The antibacterial, and moderate antioxidant properties are
treated cotton exhibited multifunctional properties reported even after 20 washing cycles. So, this eco-
like antibacterial, UV protection, antioxidant friendly approach could not only provide the silk
properties, and enhanced thermal stability. Yellow- fabric with multifunctional properties but also
brown shades were shown by the treated cotton impart colour56.
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 487

6.2.10 Grape Skins and Seeds product is applied to silk fabric using the exhaustion
Grape skins and seeds, a low-value by-product technique in acidic conditions (pH 3 at 90°C). Brown
from the wine industry, are rich in polyphenolic colour, along with good flame retardant properties, is
compounds. Grape seed proanthocyanidins (GSP) are imparted. Caramelized solution (1%) imparts self-
also utilized to impart colouration, antibacterial and extinguish functionality, and if taken in an adequate
flame retardant properties to silk fabric. The treated amount, it could provide a semi-durable flame-
silk fabric is yellowish-brown and displayed resistant finish to the silk fabric. The property of
acceptable colourfastness to washing, perspiration, bubbling upon heating the caramel is responsible for
and rubbing, but poor light fastness. To improve the theflame retardant properties of the treated silk. Also,
light fastness, post-mordanting is suggested as an the intumescent char layer is formed onto the treated
option. An improved flame retardancy along with fabric, revealing a condensed charring mechanism.
increased thermal stability and the charring ability of However, a slight adverse effect on tensile strength
silk are also reported by researchers. The treated silk and handle of treated silk fabric is also observed59.
fabric showeda condensed phase mechanism of flame Results in terms of add-on percentage and LOI of
retardancy. It is also reported that with an increase in some research works reported for flame retardant
GSP dosage, the LOI is improved, while damage finishing of various textile materials using plant-based
length is decreased57. extracts are summarised in Table 3.
6.2.11 Phytic Acid along with Biochar 7 Flame Retardant Finishing Using Intumescent Systems
Phytic acid and biochar were also applied on cotton The intumescent-based flame retardants are special
fabric to reduce its flammability. Phytic acid is a cases of the solid (condensed phase) mechanism. A
phosphorus-based compound obtained from a natural thermally stable char layer is generally formed, which
plant source, while biochar consists of carbon and is acts as a barrier when a heat source irradiates an
obtained from biomass. An aqueous mixture of phytic intumescent material and reduces flammability. An
acid and biochar (1:1 weight ratio) is applied to the intumescent system/material consists of three major
cotton fabric. This bio-sourced system enhanced the components: an acid source, a carbon source, and a
flame retardancy, and the final add-on on the fabric is blowing agent. However, the limited durability of the
just 8 wt. %. A self-extinguishing behaviour is attained coated textiles and enhanced stiffening are the major
by the treated fabric, and even under the exposure of 35 issues being encountered with such formulations60.As
kW/m2,the fabric did not ignite. The treated fabric reported in the literature, some intumescent flame
exhibited poor wash fastness, but the washed fabric retardant formulationsfor different textile materials are
showed better fire-resistant properties58. summarised in Table 4.

6.2.12 Caramel product 8 Prospective Flame Retardant Coatings by

Caramel product obtained after heating glucose in Hydrogels
alkaline conditions (sodium hydroxide) imparts flame The already prevailing flame retardant polymer
retardant properties to silk fabric. The caramel fabrics such as aramids are not widely used as these
Table 3 — Summary of application of plant-based resources for FR finishing of textiles
Natural plant-based resources Fabric Addon, % LOI, % Ref.
Spinach leaves extract Cotton 3.5-8 26-30 43
Banana pseudostem sap Cotton 2-4.5 26-30 44
Wool 3-5 29-35 7
Phytic acid Wool - 28-35.2 8
Silk/wool blend - 29 45
Green coconut shell extract Cotton 4.12-5.97 23-31 46
Jute 4.92-9.18 25-38 47
Wool 6.89-10.9 30-36 48
Nucleic acid Cotton 8 - 49
Pomegranate peel extract Cotton - - 53
Tea stem waste Silk - 26.3-26.75 55
Phytic acid and biochar Cotton 4-10 - 58
488 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

Table 4 — Some intumescent flame retardant formulations on different textile materials

Intumescent flame retardant Textile Flame retardant Additional property Ref.
formulation material properties
Modified I-type ammonium Cotton  LOI 50.1 (30% APP)  Excellent durability against 61
polyphosphate (APP) +dicyandiamide  LOI 28.5 after 50 washes washing
(catalyst) using P-O-C covalent bond  No after-flame or afterglow during  Physical properties retained
vertical burning after treatment
 Reduced peak heat and total heat
release rate
 Good flame retardancy
Poly hexamethylene guanidine Cotton  Increase in residue Antimicrobial effect against 62
phosphate + ammonium  No afterglow E. coli and S. aureus
polyphosphate using layer-by-layer  Intact weave structure in the vertical
assembly burning test
Positively charged chitosan (CH) Polyester  After 10 BL, the anti-dripping - 63
+ negatively charged ammonium property improved
polyphosphate (APP) using layer-by-  LOI value improved (25.5)
layer technology  Even char production
Vinylphosphonic acid (VPA) Cotton  Stable char layer formed after burning The Durability of the 64
+ methacrylamide (MAA) + potassium  Self-extinguishing effect observed in treated fabricob served after
persulphate as a radical initiator the horizontal flammability test 5 wash cycles
 Weight loss after the first wash but
later not observed
Polyethyleneimine (PEI) wrapped Cotton  Good fire-retardant properties  Excellent hydrophobic 65
nano-silica + polyphosphoric acid  LOI 28.2 properties with a contact
(PPA) using layer-by-layer technique  Increase in thermal stability angle of 142° ±1°,
followed by dip pad cure coating attained with 41% of char yield at  Reduction in breaking
with water-repellent chemical 600°C, 9.2 cm char length, strength moderate
 No after-flame and after-glow
detected
Polyelectrolyte polyethyleneimine Ramie  Self-extinguishing behaviour of - 66
(PEI) + ammonium polyphosphate fabric when tested for vertical
(APP) using layer-by-layer technology flammability
 Fire retardant properties and thermal
properties obtained
 Higher char residue at 400°C - 600°C
as compared to the control fabric
Phenylboronic acid (PA) and branched Cotton  Add-on of 33.8 % provided self- Semi-durable coatings 67
polyethyleneimine in acetone chemical extinguishing behaviour; obtained
using the dipping process followed by  LOI got enhanced
crosslinking  Total heat release rate reduced
compared to that of the control fabric
Negatively charged ammonium Cotton  20 BL of formulation sonicated and - 68
polyphosphate + positively charged non-sonicated imparted flame
chitosan using layer-by-layer assembly retardant properties to treated
with ultrasonication rinsing after each fabric
layer deposition
Ammonium polyphosphate, Nylon-6.6  Prevented melt dripping for treated The formulation could be 69
pentaerythritol and melamine fabric used for curtains and
 Above 13% char residue, which could carpets where wash
even reach 24% at 750°C durability is not needed
 LOI of 27.9
(contd.)
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 489

Table 4 — Some intumescent flame retardant formulations on different textile materials (contd.)
Intumescent flame retardant Textile Flame retardant Additional property Ref.
formulation material properties
Phosphorylated sodium alginate, Isotactic  Flame retardant properties and - 70
dipentaerythritol, and ammonium polypropylene thermal stability achieved
polyphosphate by melt blending into  Heat release rate and total heat
fibre release reduced drastically along
with smoke suppression (-76%)
Sodium polyphosphate, poly(allylamine) Polyester and  Reduction in peak heat release rate - 71
(PAH), and TiO2 nanoparticles using polyamide observed for polyamide fabric
layer-by-layer technology (-26%), while for polyester fabric,
alimited effect reported
Cationic branched polyethylenimine Cotton  Enhancement in thermal stability - 72
with urea + anionic clay nanoparticles  Decreased heat release rate and
using layer-by-layertechnique increased burning time
Chitosan, ammonium polyphosphate, Polyester -cotton  Reduction in flammability - 73
and silica using layer-by-layer blends  Afterglow suppression along with
technique (quad-layer formed) an increase in char residue
Ammonium polyphosphate, branched Cotton Tri-layer coating produced a char Superhydrophilicity, 74
poly (ethylenimine), and fluorinated- layer, along with self-extinguishing along with self-healing
decyl polyhedral oligomeric behaviour property
silsesquioxane
Cationic polyallylamine along with Polyamide 6.6 40 BL coated sample showed a - 75
anionic sodium polyphosphate using reduction in peak heat release rate
layer-by-layertechnique (-36%)
Sodium polyborate along with poly Cotton  10 BL coating completely - 6
hexamethylene guanidine phosphate extinguished flame along with a
using layer-by-layer assembly decrease in peak heat release rate,
total heat release rate,
 LOI increased
Phytic acid, chitosan, and silicon dioxide Cotton Flame retardant, and water Superhydrophobicity 76
modified with hexamethyldisilylamine repellent properties, retained even imparted
after 50 abrasion cycles using
sandpaper
Cationic casein, anionic ammonium Cotton With an increase in casein, char - 77
polyphosphate residue enhanced, but comfort
properties were improper after 5
wt. % casein
Banana pseudostem sap (BPS) + boric Cotton  Banana pseudostem sap, along with - 78
acid 3% boric acid, imparted flame
retardancy
 LOI 42
Ammonium polyphosphate + phosphorus Polyester  Melt dripping after treatment for - 79
the polyester fabric prevented
are quite costly, have low decomposition temperatures, Hydrogels are hydrophilic having cross linked
and can cause burns to fire-fighting personnel. Hence, it polymeric networks, where water is the dispersing
becomes important to manufacture such fabrics, which medium. These are water-swollen and formed by the
are fire retardant and anti-burn in nature80. Due to its reaction of either a single monomer or between two
high specific heat capacity and latent heat of monomers. These have a special ability to swell and
vaporization, water makes it an excellent fire retain water but do not dissolve in water. The
extinguisher. However, water cannot be used as it exists hydrophilic functional groups linked to the
at room temperature in a liquid state with no fixed shape. polymeric chains are the reason that hydrogels
Hence, for resisting fire, hydrogels have been discovered absorb water, whereas they resist the dissolution in
that are quite effective and can be used to prepare fire water due to the crosslinks that are formed between
fighter’s protective clothes81,82. the chains83.
490 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

The hydrogel can function as a fire-retardant Polyisocyanate, a water-soluble prepolymer when

coating due to its very high water content. It can dissolved in either a solution of an intumescent or a
absorb a huge amount of heat energy and release it flameretardant material or an aqueous slurry, had
when evaporation occurs. The combustibles, when been reported to produce flame retardant protective
coming in contact with the water vapour, instantly coatings. The gel prepared can impart a coating that
form an oxygen barrier layer, and further stop the could save it from a flame source. The crosslinked
combustion process by reducing the polyurethane coating can produce solid content on the
temperature81,82.Various hydrogels, found to be flame material85.
retardants, are discussed in this section. In another study, the xanthan gum (XG) is used
The physically crosslinked hydrogels of to prepare a green hydrogel, which functions as a
Li-alginate/ poly(acrylamide-co-stearyl methacrylate) flame retardant solution and is sprayed to prevent
are reported to behave as an excellent and tough forest fires. It was also detected that to increase the
flame-resistant material. The obtained flame-resistant effect, intumescent formulation with resorcinol
hydrogel can sustain the flame at even 1300°C for 50 diphenyl phosphate (RDP) (acid source) and starch
s. It is also reported that even if the prepared hydrogel (charring agent) was used along with xanthan gum
is scratched, it can recover back and show self-healing as a coating. It is reported that the formulation can
properties. As hydrogels possess the property to retain stop the self-combustion of the grass86.
water, they could last for around 6 months or even Poly (N-isopropylacrylamide), SA, and poly
more. So, the Li-alginate/ poly(acrylamide-co-stearyl (vinyl alcohol) are reported to form a triple network
methacrylate) hydrogels could be used for making hydrogel onto the cotton fabric. The prepared
flame-resistant coatings for fireproof fabrics, and for hydrogel-fabric laminate can impart excellent flame
protection to trees and the buildings structures81. retardancy. When exposed to a flame source, the
Poly (N-isopropylacrylamide), sodium alginate
hydrogel-fabric laminate is intact for 12 s. The
(SA), and silver nanoparticles are also reported to
obtained hydrogel displayed excellent swelling
form a physical interpenetrating polymer network
ratio, swelling and deswelling behaviour, and
(IPN) on cotton fabric. It is observed that prepared
antibacterial properties. SAis even able to enhance
IPN hydrogel could hold water up to 2186% at 20°C,
the water retention properties of the hydrogel. The
thus exhibiting an excellent ability to absorb the heat
thermal stability of the prepared hydrogel is
when the water got evaporated. It is also revealed that
best when SA and poly (vinyl alcohol) are in a
the prepared IPN hydrogel shows good elastic and
strength properties. When tested by vertical ratio 2:187.
flammability, hydrogel fabric laminate cannot burn Water-soluble chitosan, acrylic acid, polyvinyl
when ignited by a flame source for 12 s, while the alcohol-based macromonomer, and copper (Cu (II))
control cotton fabric is burnt out. Due to the presence ion together are reported to form a flame retardant
of silver nanoparticles along with SA reducing agent, self-healable hydrogel. The prepared hydrogel is
it is also observed that the hydrogel fabric laminate coated onto polyester fabric. The hydrogel-coated
displays antibacterial properties (around 96%) against fabric's thermal stability is found much higher than
E. coli and S. aureus bacteria. Hence, it is concluded that of the original fabric. A decrease in the peak
that the prepared hydrogel laminate could be used to heat release rate for the hydrogel-coated fabric
produce the firefighter protective clothes82. isobserved. The hydrogel-coated fabric can self-
Starch grafted with butyl acrylate (BA) to form extinguish when tested for vertical burning88.
starch-g-poly (butyl acrylate) (PBA) is reported to form Chitosan-grafted poly (acrylic acid-co-
a hydrogel structure that can hold a huge amount of methacrylamide) hydrogel is also prepared for the
water. This prepared hydrogel, along with mica mine-fire fighters. The water absorbance capability of
(layered aluminium silicate),are reported to impart the prepared hydrogel is enhanced due to the grafting
flame retardancy. The obtained bio-nano composite is of chitosan in an acidic solution as well as in
found to be biodegradable, along with the added deionized water. Water retention is enhanced for the
benefits of thermal stability and water absorbency. The prepared hydrogel. The prepared hydrogel prohibited
prepared bio-nano composite on wood could delay the the initial oxidation of coal. So, it is an excellent
ignition time, reducing the peak heat release rate84. mine-fire retardant material89.
 KAKAR et al.: FLAME RETARDANT FINISHING OF TEXTILES–A COMPREHENSIVE REVIEW 491

Table 5 — Flame retardant coatings on different textile materials produced by other processes
Flame retardant formulation Method Textile material Flame retardant properties Ref.
Tri(acryloyloxyethyl) UV curing Cotton Decrease in peak heat release rate, heat release 90
phosphate (TAEP) and triglycidyl rate, and total heat of combustion observed, an
isocyanurate acrylate (TGICA) increase in LOI value for coated fabric
Vinylphosphonic acid and acrylamide UV curing Cotton With an increase in acrylamide concentration, 91
comonomers the flammability further reduced, enhancement
in LOI (32) , with self-extinguishing behaviour
even at 5 laundering cycles
Positively charged alumina coated silica Spray-assisted Polyester Anti-dripping observed, with an increase in 92
with negative charged unmodified silica (horizontal) time of ignition, reduction in heat and smoke
layer by layer produced and incorporation of more uniform
coating
Para-phenylene One-step spray Cotton Water-based coating of phosphorus nitrogen 93
diamine (PDA) along with process combined formulation showed reduced
tetrakis(hydroxymethyl) phosphonium flammability along with self-extinction within 3 s
chloride (THPC)
Silica-based layer-by-layer assemblies Dipping, Cotton Horizontal spraying systems gave better 94
horizontal, homogenous coating layer, provide best flame
vertical, and retardant properties compared to vertical and
spray coating dip method
Diammonium hydrogen phosphate Micro- Cotton Durable flame retardant coatings, intumescent 95
(DAHP) microcapsules on polyurethane encapsulation
shell
(3-Glycidyloxypropyl triethoxysilane Sol-gel Cotton Coating self-extinguishing in nature, imparts 96
modified N-(phosphonomethyl) technique flame retardant properties, reduction in heat
iminodiacetic acid (PGPTES) + release rate
tetraethylorthosilicate (TEOS)
Phytic acid and urea + Sol-gel Polyacrylonitrile Flame retardant properties with thermal 97
tetraethoxysilane (TEOS) technique (PAN.) stability, self-extinguishing behaviour for
treated fabric, enhanced LOI (42.1)
Nitrogen-modified silane Sol-gel along Cotton Reduced thermal stability, enhancedchar 98
hybrid + phytic acid with layer-by- formation, 15 BL extinguish flame completely
layer technique with a reduction in peak heat
(-31%) and total heat release rate (-38%)
Succinic acid, malic acid, and Pad-dry-cure Cotton Succinic acid more efficient flame retardant 99
tartaric acid (TTA) than malic and tartaric acid
Zirconium Exhaustion Wool Treated wool shows higher 100
oxychloride optimized procedure LOI than untreated

9 Other Flame Retardants chemistry are efficient flame-retardants, some are

Various coatings for imparting flame retardancy to known to have adverse effects on the environment,
different textile materials have been reported to be health and safety. Various innovative techniques
produced by UV curing, microencapsulation, spray like nanotechnology, plasma, LbL, and
coatings, and sol-gel methods. Some of them are intumescence have been explored. However, due to
summarised in Table 5. current trends in greener methods and
environmentally safe products, it has become
10 Conclusion essential to explore sustainable and green coatings
In order to protect textile materials and their to produce flame retardant textiles. Although
users from fire hazards, a flame retardant finishing hydrogel is found to be an efficient flame
is an ideal approach. Variety of attempts have been retardant, it is explored to a limited extent in the
reported in the literature which are reviewed and flame retardant finishing of textiles.
reported in this paper. Although traditionally used The exploration of sustainable flame retardants
compounds based on halogen, phosphorus, for imparting efficient and durable flame
phosphorus-nitrogen, borax, and boric acid retardant textiles at low add-on levels will remain
492 INDIAN J. FIBRE TEXT. RES., DECEMBER 2023

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