Conference PaperPDF Available


Fire retardants & textiles: past, present and future
15-16 February, 2016 Torino - Italy
S. Giraud, F. Rault, A. Cayla, F. Salaün
Université Lille Nord de France, F-59000 Lille, France
Ecole Nationale Supérieure des Arts et Industries Textiles (ENSAIT)/Laboratoire Génie des
Matériaux Textiles (GEMTEX), F-59100 Roubaix, France
Abstract: Textiles are materials that exhibit extremely varied forms and are used for a variety of applications
where fire protection is essential.
Textile with wood was historically one of the first flame-retardant materials. FR
products for textile materials presented the same evolution as those of general polymeric materials even though
adaptations are necessary to meet the specific characteristics of the fibrous material and its industrial
Keywords: Textile, Flame Retardant, History, Industrial Requirements
The fibrous materials exhibit extremely varied forms for application domains that are not limited only to
clothing. Some of these high-value products are multifaceted, ie multifunctional (protection against all
types of threats), intelligent (integrating sensors), reinforcing structures for composites, insulation for
buildings, implants for medical, etc. Heatproof and flame retardant (FR) textiles have applications not
only for protective clothing, but also in areas where fire protection is essential, i.e. public transport, or
places open to the public. These materials fall into the composition of multiple products for furniture,
bedding, seat covers, housing (wall coverings), structural composite materials, filters, acoustic and
thermal insulation panels, etc. The textile fire behavior
and the associated fireproofing principles
have already been the subject of numerous bibliographic summaries.
From a historical perspective, the first patent with FR use was deposed in 1735 by Obadjah Wyld and
concerned the textile and paper. In 1820, Gay-Lussac suggested a mixture of ammonium phosphate,
ammonium chloride and borax to increase the fire retardance of textiles used in French theaters.
During the twentieth century, advances in chemistry have obviously revolutionized the textile industry.
Synthetic fibers appear and some have intrinsic properties of fire resistance (eg marketing in 1961 of
Nomex® the first polyaramide). The major classes of FR products have been adapted and formulated
to treat various fibers and meet the specific requirements of the textile material (eg development in
1955 of the first sustainable flame retardant cellulosic fabric via Proban®). The use of FR products
have undergone changes as the abandonment of certain brominated components for their
environmental impact. These evolutions have of course also affected the treatment of textile materials.
The fire behavior of fibrous materials has number of peculiarities. Textiles compared to plastic
materials generally have a large surface area, thus promoting exchange with oxygen. Thereby textiles
have short ignition time and high flame propagation speeds. Their propensity to initiate and propagate
the fire makes "hazardous", even if their heat release rate could be quite small due to their low
density. The fire performance of a textile substrate depends mainly on the polymeric nature of the
fibers. Mineral fibers as glass by the non-combustible nature and fibers from thermostable polymers
as polyaramide are inherently fire resistant. The other categories, i.e natural or artificial (cellulose,
protein) and synthetic (polyolefin, polyester, polyamide, etc.) exhibit various fire behaviors. Cellulosic
are among the most easily ignitable fibers while protein (wool) hardly burn. Both types of fiber are
naturally charring. Synthetic fibers present a low charring behavior (polyamide) or no charring effect
Fire retardants & textiles: past, present and future
15-16 February, 2016 Torino - Italy
(polyolefin). In addition, synthetic fibers tend to escape the flames, and generate the hazard of falling
material in the molten state or inflamed with risk of direct burning and fire spread.
Industrial requirements on FR textiles are related to legislation and standards which define the
required levels of fire resistance specific to the application sectors. Fireproof textiles must also meet
the requirements and specific industrial constraints. In addition, many features need to be compatible
with fireproofing, i.e. (i) Dry or high temperature cleaning resistance; (ii) maintain comfort (color, touch,
management of heat and mass transfer); (iii) mechanical resistance for protective clothing, seat
covers, structures for buildings, or otherwise; and (iv) specific properties to an application area
(filtration, sound insulation, weather resistance, resistant to fungal growth, etc.). Thus, the main
industrial challenges for flame resistant textile development can be namely summarized in four points,
(i) to reach the level of fire retardancy at lower cost; (ii) to design in the context of sustainable
development; (iii) to make the textile a fire resistant protective layer; and (iv) maintain the FR
properties with other expected features.
Figure 1 : summary diagram of textile fireproofing strategies
The main classes of flame retardants for polymeric materials are also in the fibrous materials with
certain adaptations. Figure 1 summarizes the different strategies for fireproofing a fibrous material.
None of the existing commercial strategies not yet fully meet the challenges outlined above.
The first option to design a FR fibrous material is the selection of fibers having this property. Mineral
fibers are for very specific applications (eg reinforcement materials), while they are inherently non-
combustible and have high mechanical properties. Their lack of comfort and high cost of manufacture
and / or implementation mean that they are never used directly for traditional applications (eg furniture
cover), or while being hidden and in combination with other fibers. The thermostable fibers, fire
resistant and mechanically efficient, are also limited in their use by their cost, low comfort (hard color
management) and their aging problem (particularly UV). FR fiber from polymers chemically modified or
containing fillers have a better compromise (cost, comfort, implementation, washing resistance) but
does not ensure alone protection and fire resistance equivalent to the heat-stable fibers. The three
main commercial examples are the Lenzing viscose FR® the Modacrylic (Kanecaron) and polyester
Trevira CS®.
The second way to give FR properties to a textile is to add a surface treatment. This is the only
possible strategy for natural fibers. Thus, for several decades, many R&D efforts have focused on
cellulosic textiles including cotton which remains one of the most used fiber in the world. Surface
treatments can be divided into two categories, i.e. the non-reactive and reactive. The former are
Fire retardants & textiles: past, present and future
15-16 February, 2016 Torino - Italy
mainly based on phosphorus and nitrogen compounds, inorganic or organic, which are fixed by weak
bonding on the substrate, or blocked by a polymer resin (binder). These treatments are generally
inexpensive and simple to implement, but have the disadvantage of being at best semi-durable.
Among these treatments, there is the principle of back coating, ie depositing a layer of flexible polymer
(acrylic, polyurethane) FR (especially with an intumescent formulation) on the non-visible face of the
textile. Although the durability of this technique is not optimal, it has the advantage of being used on
any textile nature including mixtures of fibers. The reactive treatment, as Pyrovatex® and Proban® the
two most famous processes for cellulose, are permanent (resistant to washing). However, their
implementation remains complex and alteration of mechanical properties of textile is sometimes
Among the most recent developments in research on fireproofing textiles, two processes have been
studied, the Layer-by-Layer (LbL) method and sol-gel process. Alongi et al.
have summarized all the
work for the processes applied fireproofing primarily cellulosic textiles. The LbL process seems for
now difficult to apply industrially since it has little durability (FR product loss by simple manipulation of
the textile). The sol-gel process, more promising (10 washes resistance), requires extremely long
implementation times, incompatible with industrial production. For ten years, our laboratory contributes
to the development of solutions in the field of fireproof of textiles in connection with the expected
industrial challenges. The main strategies developed are (i) the reformulation and / or improvement of
fire retardant for textile applications through the microencapsulation process
, (ii) the incorporation of
fillers (micron or nanometer) during the melt-spinning in particular for polyester to develop upholstery
fabrics able to withstand the heat and to protect the whole of the material
, and (iii) the use of
additives and / or bio-based polymers for the development of flame retardant textile
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retardant polyurethane coating for polyester, 2013, 14th European Meeting on Fire Retardancy and Protection of Materials,
Lille, France, 01-04 July
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fillers in bio-based polymers (PA11 and PLA), 2015,Eurofillers Polymer Blends, Montpellier, France, 26-30 April
... Although instilling flame resistance has been a subject of interest since the ancient Egyptians [1], "modern" chemists have only been on the case since the 18th and 19th centuries, as evidenced by the words of American poet Emily Dickinson [2]: "Ashes denote that fire was-revere the grayest pile, for the departed creature's sake, that hovered there awhile-fire exists the first in light, and then consolidates, only the chemist can disclose, into what carbonates." The same era saw the publication of landmark work by French chemist Joseph Louis Gay-Lussac (who studied flame resistance with the intent of protecting theatres) and Scottish chemist M. M. Pattison Muir, who published The Chemistry of Fire in 1893, only a few years after Emily Dickinson's death [3][4][5]. In the century-and-a-half since, our understanding of the molecular world, as it pertains to fire, has progressed significantly and the scientific community has made tremendous advances so that chemists can fully disclose into what carbonates. ...
... Early commercial examples include: Bakelite, Nomex, Kevlar, and others. [3] This is understandably an important topic of industrial and academic research considering that structure fires cause $6.7 billion worth of damage, 12,300 injuries, and >2500 deaths annually in the United States alone [6]. The massive California wild fires in the summer and autumn of 2018 were a stark reminder of the threat that fires pose. ...
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It would be difficult to imagine how modern life across the globe would operate in the absence of synthetic polymers. Although these materials (mostly in the form of plastics) have revolutionized our daily lives, there are consequences to their use, one of these being their high levels of flammability. For this reason, research into the development of flame retardant (FR) additives for these materials is of tremendous importance. However, many of the FRs prepared are problematic due to their negative impacts on human health and the environment. Furthermore, their preparations are neither green nor sustainable since they require typical organic synthetic processes that rely on fossil fuels. Because of this, the need to develop more sustainable and non-toxic options is vital. Many research groups have turned their attention to preparing new bio-based FR additives for synthetic polymers. This review explores some of the recent examples made in this field.
... This person is a British inventor that developed FR from mixing alum, ferrous sulfate and borax that used for treatment in papers and fabrics to prevent the spread of flames [12]. In year 1820 a French guy name Gay-Lussac used the mixture of ammonium phosphate, ammonium chloride and borax to increase the flame retardant of textiles used in theaters [13]. He also considered as a pioneer person in invented a bio-based flame retardant on fabric using hemp flax weave treated with borax and ammonium polyphosphate or APP [12]. ...
Due to thermal and flame/fire sensitivity of biopolymers especially in plant-based biopolymer fillers, it is extremely and necessary to improve the reaction to flame. The bio-polymers currently are used in many applications and daily life products and due to the potential risks of its tendency to burn and widespread the flames. To overcome these risks, an introduction of flame retardant (FR) compounds, additives, or fillers based on organic and inorganic approaches such as nitrogen-based FRs, halogenated-based FRs, and nano fillers have becoming significant incorporated into biopolymers. Most traditional uses of FRs that involve halogenated and inorganic FRs are toxic and non-biodegradable during disposal. Thus, the need to look for more environmentally friendly FRs such as nanocellulose, lignin, and others have become crucial. Because of concern on environmental and human health issues the biopolymers becoming a popular subject nowadays among scientists and researchers. The aim of this review paper is to promote the use of biodegradable and bio-based compounds for flame retardants with reduction in carbon footprint and emission. Furthermore, the addition of bio-based FRs are significant in preventing and reducing the spread of flames compared with conventional FRs. A detailed discussion on the flame retardants mechanism, characterization techniques, morphology correlation and various biopolymers with flame retardants are also discussed.
... In contrast with plastic materials, textiles produced from cellulose-based materials have a larger surface area, thus promoting exchange with oxygen. Therefore cellulose-based textiles have shorter ignition time and high flame propagation speeds (Giraud et al., 2016). When it burns, it will generate temperature of approximately 300 CÀ400 C and release toxic flammable gases (levoglucosan, pyroglucosan, etc.) which can cause serious health risks other than damaging the textile itself (Basak, 2018). ...
Cellulose-based textile fibres have rapidly evolved since their first invention. It is an important source of reference in textile industries due to their universality and compatibility. Over time, the transition from natural to man-made fibre involved extensive research developments. By virtue of the better development, modification of native cellulose is not foreign in textile industries and offers a slew of benefits. Nonetheless, inventions were meant to meet current needs. Such needs include aesthetically pleasing and high mechanical strength, with low production cost. Current trends are into technological advancement providing textiles with self-heating and self-cooling properties, embedded with electrical devices, as well as, but not limited to, antibacterial property. Man-made cellulose-based textile has more to offer in comparison to native cellulose. However, all these advancements are still limited with renewability and sustainability. Both industries and consumers are the drivers to possibilities in the developments of textile technology.
... In the past, compounds like plaster of Paris (gypsum), alum and ammonium were used to make fire-resistant fabrics [3]. It was after the notable discovery of boron in the 1800s that the textile industry acquired a great demand for developing new flame retardants [4,5], which would not get washed off even after repeated washing. Later, halogenated and phosphorus-based organic-and inorganic-based chemicals acquired a robust demand as they easily suppress oxygen by producing a major volume of non-flammable gases and they formed a glass coating throughout due to thermal disintegration [6]. ...
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We have developed functionalized graphene oxide (FGO) nanocomposites-based intumescent flame-retardant coating. The graphene surface was functionalized by potassium carbonate by reacting graphene oxide (GO) and potassium carbonate (K2CO3). The resultant coating improved the flame retardancy of the cotton fabric. The FGO nanocomposite-coated fabric was to prove the flame retardancy properties of the FGO nanocomposite, by detail flame tests such as limiting oxygen index, vertical flammability test and exposure to the Bunsen burner flame (~ 1500 °C) test. FGO-coated material, when exposed to fire, was observed to maintain its original shape with the release of little smoke initially and later developed char-like material. Prepared materials were characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The cotton fabric alone burnt in 5 s, but when coated with the FGO, it was able to withstand the fire for more than 325 s (5.25 min), whereas the only GO- and K2CO3-coated fabrics were completely burned out within 10 s and 20 s, respectively. This obtained FGO nanocomposite coating is proved to be an efficient flame retardant with an easy, simple one-pot and inexpensive technique in comparison with the reported works. Graphic abstract In this work, we have synthesized functionalized graphene nanocomposites, which act as an efficient flame retardant. The recent process established that this is a simple and eco-friendly method for efficient graphene-functionalized IFR.
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Non-durable and semi-durable flame retardants based mostly on phosphate or phosphonate salts continue to be used on infrequently washed or disposable goods, and recent improvements have been made to impart better `hand' or some limited wash resistance. Backcoating with insoluble ammonium polyphosphate, usually with additives and binders to provide intumescence, has been found effective on charrable fabrics. However, the leading backcoating effective on a wider range of fabrics, including synthetics and blends, is decabromodiphenyl ether plus antimony oxide. Newer candidates in development for textile coating are polymers and copolymers of pentabromobenzyl acrylate. The leading durable finish for cellulosic fibers, in use for about 50 years, continues to be based on tetrakis(hydroxymethyl)phosphonium salts reacted with urea and cured with gaseous ammonia. Softer versions have been recently developed using chemical or process modifications, or using selected fiber blends. Somewhat less durable phosphonic ester methylolamide finishes, not requiring gaseous curing, are used on cellulosic fabrics, especially overseas. Other competitive wash-durable phosphorus-based finishes for cellulosics and blends are in development. Polyesters continue to be flame retarded using a phosphonate or hexabromocyclododecane in a `thermosol' process. Polyesters with built-in phosphinate structures are available as specialty fabrics. A dialkylphosphinate salt has been recently introduced as a melt spinning additive in polyester. A tribromoneopentyl phosphate melt spinning additive has been developed for polypropylene fiber. A number of inherently flame retardant synthetic fibers recently achieving increased usage include melamine-based fiber, viscose rayon containing silicic acid, aramides, oxidized polyacrylonitrile, and polyphenylene sulfide fibers. Some of these are used in protective clothing. The recent California and Federal mattress open-flame test standards have brought barrier fabrics into prominence. Some of these barriers use boric acid on cotton batting, others are proprietary composites and blends, both woven and nonwoven, comprising inherently flame retarded fibers combined with lower cost non-flame-retardant fibers. Upholstered furniture open-flame standards are pending.
The present paper is aimed to review the state of the art on the novel and emerging techniques recently developed in the textile field for conferring flame retardant properties to natural and synthetic fibres. In particular, a comprehensive description of the results achieved by depositing (nano)coatings on the fabric surface through nanoparticle adsorption, layer by layer assembly, sol–gel and dual-cure processes, or plasma deposition is presented. Finally, the unexpected and recently achieved results in the use of proteins and nucleic acids are discussed.
Conference Paper
Intumescent formulations using different bio-based carbon sources were prepared and added into polyurethane coating before application on polyester textile fabric. The flame retardant properties of such textile fabric have been investigated by cone calorimeter test and UL-94. The results of cone calorimeter show a marked decrease of the peak of heat release rate (PHRR) of coated fabrics compared to uncoated fabric.
A microencapsulated flame retardant with a melamine-formaldehyde shell was prepared by in situ polymerization, then incorporated into an iPP matrix with a coupling agent to manufacture multifilament yarns by melt spinning. The influence of the post-treatment on the resulted microcapsules with an alcoholic solution was also studied. The spinnability of these formulations based on the interface characterization from contact angle measurements, tensile test and thermal characterizations was explored to determine the maximum draw ratio (DR) to apply. Finally, knitted fabrics were processed from multifilaments, and their flame-retardant properties were evaluated by performing fire tests according to the FMVSS 302 and Din 4102 part B experiments. The different mechanical and thermal behaviors were discussed in terms of the influence of the DR and the post-treatment applied on fibers during the spinning process and during the recovery of the microcapsules, respectively. The results showed that it was possible to obtain multifilament yarns with a DR of 4, but the best properties were obtained with a DR of 3 and for un-treated microcapsules. Furthermore, the samples containing un-treated microcapsules reach a B rating at the FMVSS test with a fast flame progression and a very low duration of burning. Copyright © 2012 John Wiley & Sons, Ltd.
Three types of microcapsules of di-ammonium hydrogen phosphate (DAHP) with different polymeric shells were evaluated as flame retardants in commercial polyurea padding for textiles. Encapsulated FR agent has the advantage of being compatible with the polymer matrix. The thermal degradation for the three types of DAHP microcapsules shows that our microcapsules act as intumescent fire retardants. The reaction to fire of polypropylene fabrics padded with FR polyurea loaded with neat DAHP or microencapsulated DAHP was studied with the cone calorimeter as a fire model.
In this study, PET multifilaments containing blends of aluminium phosphinate and different polyhedral oligomeric silsesquioxanes (POSS) were developed via melt spinning process. Textiles made by the filled fibres were then produced and their fire behaviours were investigated. Improved performances of the fibrous materials have been noticed such as a decrease in the dripping effect, in the peak of heat release rate and in the total heat evolved while combustion. Differences on the textiles fire properties were also observed depending on the used POSS nanoparticles with distinct ignition times and char protective properties.
This paper deals with the fire behaviour of poly (ethylene terephthalate) (PET) filled with Exolit OP950, a zinc phosphinate fire retardant, and three polyhedral oligomeric silsesquioxanes (POSS) having different chemical structures. Regardless of the POSS type, intumescence occurs during combustion, but the insulation properties of the chars produced are different. Best reductions on total heat evolved (THE) and on cumulative CO2 with no increase in CO emissions are observed when dodecaphenyl POSS is used. This may be related to its thermal degradation pathway, releasing via this process volatile organic species contributing on intumescence and producing an effective protective layer having a foliated structure.
Poly (ethylene terephthalate) (PET) multifilaments loaded with fire retardants were produced via melt spinning and textiles were manufactured using the latter. The fire retardance properties of the knitted fabrics were investigated showing an important decrease of heat released with presence of phosphorous-containing chemicals (Exolit OP950). Incorporation of POSS nanoparticles in PET-OP950 systems slightly decreases the fire properties of the material but acts as good smoke suppressor with release of low toxic fumes while combustion.
Almost 50 years ago, the 1950–1960 period witnessed the development of the chemistry underlying most of today’s successful and durable flame retardant treatments for fibres and textiles. In today’s more critical markets in terms of environmental sustainability, chemical toxicological acceptability, performance and cost, many of these are now being questioned. “Are there potential replacements for established, durable formaldehyde-based flame retardants such as those based on tetrakis (hydroxylmethyl) phosphonium salt and alkyl-substituted, N-methylol phosphonopropionamide chemistries for cellulosic textiles?” is an often-asked question. “Can we produce char-forming polyester flame retardants?” and “Can we really produce effective halogen-free replacements for coatings and back-coated textiles?” are others.These questions are addressed initially as a historical review of research undertaken in the second half of the twentieth century which is the basis of most currently available, commercialised flame retardant fibres and textiles. Research reported during the first decade of the twenty first century and which primarily addresses the current issues of environmental sustainability and the search for alternative flame retardant solutions, the need to increase char-forming character in synthetic fibres and the current interest in nanotechnology is critically discussed. The possible roles of micro- and nano-surface treatments of fibre surfaces and their development using techniques such as plasma technology are also reviewed.