FLAME RETARDANT FINISHES

• what are Flame Retardants(FR)?

• History and introduction
• Importance of flame retardants
• Factors affecting the flammability of
textiles
• Mechanism of combustion of textile
fibres
• Classification of flame retardants
• Flame retardant finish for different
polymers
• Different flame retardant techniques
• Application of flame retardant in
textiles
• Environmental issues with flame
retardants
 What are Flame Retardant ?
 Flame retardants are the chemicals that are supposed to
reduce the ignition and prevent fire, they are designed to
minimize the risk of fire in case of contact with a small heat
source.
OR
 A chemical applied to a fabric to impart flame resistance is
called a flame retardant.

 A fabric can be considered flame resistant if it does not burn or

does not continue to burn when subjected to a flame or heat
source.
 Flame retardancy is an important characteristics of textile
materials in order to protect consumers from unsafe apparels.
 Flame retardant finishes improve flame resistance by removing
any one or more components that are required for burning.
 HISTORY AND INTRODUCTION

 In 1632, the idea of reducing the risk of fire in theaters came

about in paris. They fireproofed plaster and clay and so the
process of creating flame resistant materials began.
 In the 18th century alum and ammonium were used to make
fabrics fire resistants. 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 20th century , other brilliant scientists perfected this
same method by incorporating stannic oxide into fabrics to
make them flame resistant.
 These techniques were used to add fire resistance to natural
fibres. Once synthetic materials started dominating the cotton
market.
 Then the discovery of Tetra(hydroxymethyl)phosponium
chloride (THPC) in 1953 advanced the process of making
fabrics resistant to flames.
 THPC could be applied to cotton, paper, plastic, paint,
furniture & other building materials.
 The history of uses of flame retardant chemicals is very old.
Borax is still used as non durable flame retardant finish and
some sulphates (ammonium and alum) are also used in non
durable purpose.
 The major limitation in flame retardent finishing is to produce an
effectie finishing with non-toxic chemicals that have on detrimental
effect on fabric comfort issue.

 1990s has seen some major innovations in development of flame

resistant fibres and thermal protective clothing for firefighters and
industrial workers.

 Today flame retardant fabrics are essential for making uniforms for
firefighters and emergency personnel to protect themselves from
flame.

Importance of Flame Retardant Finish

 Textiles is an inherent part of the interior of housing and

industries, cultural and social facilities.Most of the commercially
available fabrics are highly flammable and combustible.
Significant losses of lives and property have been a concerning
issue for many years due to unwanted fire hazards.
 Therefore systematic improvement in terms of
quality ,performance and safety of textile got significant
importance.
 The development of flame retardant property of the textiles is
becoming even more important with the increasing uses of
flammable polymers in household and industrial sectors.
Factors Affecting the Flammability of
Textiles
 The flammability of textiles depends on many factors such as
the polymer in the fibre, yarn and fabric construction, type of
chemical treatment .
 Though the flammability of a textile material is not an
interinsic property like density and heat capacity, all textilr
can burn if they are exposed to the flame in right condition.
 Flammability of the material with increased supply of oxygen
favour the fire growth.

SOME FACTORS ARE AS FOLLOW :-

 Fabric construction
▫ Fabric constructions are considered as one of the major
factors during thermal protective measurement.
▫ But it is true that a combination of non-flammable fiber with
optimum construction should be used to achieve maximum
non-flammability of the textile materials.
▫ An open constructed fabric may allow the excess of oxygen
which can result more combustion and faster flame
propagation.
▫ Open end spun yarn causes increased flame propagation
compared to ring spun yarn due to scattered fiber orientation
at the yarn core and lower density .
▫ The fabric made from blend fiber can may behave quite
differently. But fabric made from cotton–polyester blend
burn more rapidly because polyester gets support from the
cotton fiber here to burn.

 Textile Fibres
▫ The flammability property of textile materials depends on the
fibre types.

▫ The flammability property of the fibre can be classified as follow-

I) Readily flammable
II) Moderately flammable
III) Non flammable

▫ Cotton, acatate, triacetate, rayon etc. Are ignite very readily

are known as readily flammable fibres.
▫ There are some fibres those are difficult to ignite are known
as moderately flammable fibres.
▫ Wool, modacrylic and aramids will not combust after removal
from the flame are known as non flammable fibres.

 Types of Polymer
▫ The flammability of the textile materials is mostly determined
by the polymer composition of that material.

▫ In designing the flame retardant materials understanding the

thermal behaviour of the polymer in the presence of
additives is considered as one of the crucial factors.
 ▫ The flammability of any polymer is mostly affected by the
physical and chemical changes of that polymer in fire and
these changes depend on the physical and chemical
structures of the polymer.

Mechanism of combustion of textile fibres

combustion is an exothermic reaction and it requires three
essential ingredients: heat,
oxygen and
fuel
Each of those components is essential for maintaining the flame,
therefore the flame-retardant agents need to interfere with one
or more of these components.

▫ Before understanding the mechanism of the flame-

retardant agents, we need to understand the mechanism of
combustion. Therefore, we would be able to understand
how flame-retardant agents can perform different role
depending on different types of combustion.
Fig : Mechanism of combustion cycle of fiber

▫ During burning the polymer gets heated and its temperature

increases, when it reaches to pyrolysis temperature it
decomposes and gives non-flammable gases, chars, tars and
flammable gases. At one point of this process the
combustion temperature is achieved.
▫ At the combustion temperature the flammable gases
combine with the oxygen which is basically a free radical
reaction.
▫ This is a highly exothermic reaction which releases a very
high amount of heat and light energy.

Classification of flame retardants

 Flame retardants are the chemicals that are supposed to reduce
the ignition and prevent fire.
According to the mode of action the flame retardants can be
classified as:
i) gas phase action
ii) condensed phase action
iii) others

According to the elemental composition flame retardants

can be classified into many types:
▫ halogens
▫ phosphorous
▫ boron
▫ nitrogen

i) GAS PHASE ACTION

 Evolution of reactive species is the main characteristics of gas
phase mode.
 Halogen and Phosphorous based flame retardants are mostly
fall in this group.
 By addition of antimony compound such as Sb2O3 the flame-
retardant activity of halogen compounds can be increased.
Volatile antimony compound such as SbX3 may be formed,
which can be act as an efficient inhibitor.
 It has been also found that certain phosphorous species have
gas phase action.

ii) CONDENSED PHASE MODE

 In this mode, a protective barrier is formed between the heat
source and pyrolysis polymer.
 The flame-retardant additive reacting with the polymer
during thermal decomposition results in the formation of this
protective barrier.
 The catalytic reaction of the flame retardants with the
polymer causes the decomposition of the polymer at a lower
temperature.
 In some cases, phosphoric acid may be formed from the
decomposition of phosphorous compounds, which form a
thermal insulating barrier on the surface of decomposing
polymers.
 The presence of Urea, Guanidine and Melamine, external
nitrogen additives can enhance the condensed phase action
of the phosphorous flame retardants.

FLAME RETARDANT CHEMICALS

i) HALOGEN BASED FLAME RETARDANTS

 Halogen containing flame retardants were the most effective
and general applicable flame retardants.
 The use of halogen-based retardants is being restricted due
to environmental concern though these were popular and
widely used in flame-retardant coatings.
 order of stability of these bonds are as follow: F> Cl > Br > I.
The thermal stability of fluorine is too stable to be useful.
 The thermal stability of iodine is below than the required.
Addition of a brominated or chlorinated compound may be
introduced into the polymer chain by copolymerization to
prepare flame retardants polymer materials.
 ii) PHOSPHORUS BASED FLAME RETARDANTS
 Phosphorus and its various compounds have been used as
flame-retardant for several decades.
 Environmental concern regarding the use of halogen based
flame retardants has given importance to develop
phosphorus flame retardants.
 Phosphorus based flame retardants can show both gas phase
action and/or condensed phased action hence are versatile.
 This type of flame retardants was also found less toxic and it
releases low smoke during combustion compared to other
flame retardants.

iii)NYTROGEN BASED FLAME RETARDANTS

 Nitrogen based flame retardants have become popular as

they are considered non-toxic and environment friendly.
 Guan et al. proposed phosphorus and halogen free flame
retardants for Nylon 6,6 . Guan et al. proposed a cross-linking
process of thiourea with polyamide chain.

FIG: Thiourea crosslinked polyamide chain

iv) SILICON BASED FLAME RETARDANTS

  Developing halogen free flame retardants results in a new
trend of siliconbased flame retardants.
 Phosphonate and siloxane provide bi-functionality of this
compound. While siloxane group is responsible for the cross-
linking with the cellulose the phosphonate provides the
flame retardancy.
 The durability has been checked with ASTM D6413-94
standard. It has been the found that there is still evidence of
flame retardancy even after 50 washes.
 This treatment significantly increases the thermal stability of
cotton, moreover it strongly reduces the total heat of
combustion and peak release of heat.

Flame retardant finish for different polymers

I) Flame Retardant Finish for Protein Polymer

 Wool is naturally a less flammable fiber compare to other
nature fibers.
 Hexafluoro zirconate and titanate salts based flame-
retardant finish is most famous for wool fiber.
 The flame retardancy mechanism is accomplished in
condensed phase through zirconium ions or compounds that
increase the char formation.
 Around 2% zirconium levels are needed for effective flame
retardancy.
 Another flame retardant finish for wool which provide
effective flame retardancy and is durable to dry cleaning and
 mild washing under neutral condition is the application of
tetrabromophthalic anhydride (TBPA).
 This is applied by exhaust method under anionic species and
around 10% on the weight of fabric of TBPA is required for
effective flame retardancy.

Fig : Tetrabromophthalic anhydride (TBPA).

II) Flame Retardant Finish for Synthetic Polymer

 Due to the unavailability of the reactive functional groups,
polyester is difficult to make flame-retardant by
conventional methods.
 The three commercial approaches for flame-retardant
polyesters are additives to polymer melt, flame-retardant
co-polymers, and finishing.
 All the methods have been used commercially. Phosphorus
and bromine compounds are mostly used as flame
retardants in all these methods.
 Trisdibromopropylphosphate, a phosphate ester
containing bromine is one of the most useful flame-
retardant finishes for polyester.
  This phosphate ester, the most versatile and effective flame-
retardant, could be applied by both exhaustion and padding
methods.

Fig: Tris (2,3-dibromopropyl) phosphate

Different flame retardant techniques

The main challenge for flame-retardant finish is to achieve the durability.
The commercially successful flame-retardant finishes need to consider
many factors; fabric construction, fiber type, required performance,
detrimental effect on fabric and environment.
I) Intumescent Flame Retardant Techniques
 Application of the intumescent material is one of the most successful
ways to reduce the flammability of the combustible materials.
 When heated above the critical temperature, these materials begin to
swell and expand.
 This phenomenon of swelling results in the formation of a charred layer
on the surface of the material, which stops the self combustion of the
treated materials.
 the intumescent materials have been used for flame retardancy of
building structure for a long time.

II) Layer-by-Layer Flame Retardant Techniques

  Layer-by-layer (LbL) is comparatively new method which has
comparatively less detrimental affect on the polymeric
materials.
 LbL is a technique of formation of multi-layer films on the surface
of the substrate, it can directly influence the combustion cycle.
 Thickness, function and composition of the layer can be controlled
and used for fabrication.
 This technique only requires room temperature and atmospheric
pressure as experimental condition, which means this is a cost-
effective process.

Application of flame retardant textiles

Flame-retardant textiles are found in many areas such as apparel, home,
offices, transportation, public buildings,high-performance technical textiles.
Few applications of flame-retardant finished textiles are given below:
 Sleepwear for infant, children and aged population.
 Fabrics used as upholstery and home textiles such as curtain,
carpet, bedcover, blankets, etc.
 Fabrics and fibrous components used in public transportation
 PVC based flame-retardant coated architectural textiles
 Chemically finished polyamide fibers are used in sports textiles

Environmental issues with flame retardants

 There are quite a large number of flame retardants, which
have been recognized as harmful. Many of these chemicals
have already banned or restriction has applied on their uses.
 Halogenated flame retardants are usually toxic and produce
corrosive gases during combustion.
 Formaldehyde which has been using in many flame-retardant
compounds is toxic and should not be used for finish.
 Antimony trioxide (SbO3 ) has issues about health
implications and environment.