Seminar

on
“Flame Retardent Synthetic Fibres”

By : Raghav Mehra
Mtech 1st year
Contents
•Introduction
•Why use of flame retardants?
•Burning of fibres
•Requirements for flame retardants
•Flame Retardant Mechanism
•Types of flame retardants
•Application Techniques
•Thermoplastic fibers
•Flame Retardant (FR) Pet Fibers through P-N Synergism
•Flame Retardancy Testings
•Toxicology
 INRODUCTION
Fire is the result of three ingredients:
• Heat
• Fuel
• Oxygen.

Heat produces flammable gases from the pyrolysis of polymer. Then, an

adequate ratio between these gases and oxygen leads to ignition of the
polymer.
 COMBUSTION CYCLE

The combustion leads to a production of heat that is spread out (delta H 1) and feed
back (delta H2). This heat feed back pyrolysis the polymer and keeps the combustion
going.
 The Fire Triangle

Fire: when all sides

are connected

Air (oxygen) Fuel

FIRE

Air (oxygen)
Ignition source
Fuel

No Fire: when any one side

is missing

Ignition source
Why use of Flame Retardants ?

In most cases polymers initiate or propagate fires because,

being organic compounds, they decompose to volatile
combustible products when they are exposed to heat.

In many fields such as electrical, electronic, transport,

building, etc the use of organic polymers is restricted
because of their flammability
Use of synthetic polymers has greatly increased. In order to
lower the "fire risk" and the "fire hazard“ of these synthetic
polymers. flame retardants need to be added into the
polymer.

The role of these additives is to :

•Slow down polymer combustion and degradation (fire
extinction),
•Reduce smoke emission,
•Avoid dripping
 Fire Dynamics
The goals for fire retardant can be simply stated in the following
items

1. Prevent the fire or retard its growth and spread i.e. the flash
over :
•Control fire properties of combustible items,
•Provide for suppression of the fire.

Flash over time vs fire retardant use

2. Protect occupant from the fire effects :

• Provide timely notification of the emergency,

• Protect escape routes,
• Provide areas of refuge where necessary and possible.

Smoke release vs fire spread

3. Minimize the impact of fire:
•Provide separation by tenant, occupancy, or maximum area.
•Maintain the structural integrity of property,
•Provide for continued operation of shared properties.

4. Support fire service operations:

•Provide for identification of fire location,
•Provide reliable communication with areas of refuge,
•Provide for fire department access, control, communication, and
selection.
5. To increase the escape time of persons.
 Burning of fibers

The burning behavior of the fibers depends on / determined by a

number of thermal transition temperatures and thermodynamic
parameters
Tg - glass transition temperature
Tm - transition temperature
(Tp) pyrolysis temperature and
(Tc) the onset of flaming combustion

Lower the Tc (and usually Tp) and hotter the flame, more flammable
is the fiber
 Limiting Oxygen Index (LOI)

LOI (limiting oxygen index) measures the inherent burning character

of the material.

•Fibers that have a LOI values of 21 or below ignite easily and burn
rapidly in air (20.8% O2).

•LOI values above 21 ignite and burn more slowly.

•When LOI values rise above 26-28, fibres and textiles may be
considered to be flame retardant and will pass most of the flame
fabric ignition tests in horizontal and vertical direction.
 LOI values of different fibers

Fiber Tg (soften) Tm (melt) Tp (pyrolysis) Tc (ignition) LOI (%)

o
C o
C o
C C
o

Wool - - 245 570-600 25

Cotton - - 350 350 18.4

Viscose - - 350 420 18.9

Nylon 6 50 215 431 450 20-21.5

Nylon 6,6 50 265 403 530 20-21.5

Polyester 80-90 255 420-447 480 20-21

Acrylic 100 >220 290 (with >250 18.2

decomposition)

Polypropylene -20 165 470 550 18.6

Modacrylic <80 >180 >180 450 37-39

PVC <80 >180 >180 450 37-39

meta-Aramid 275 375 410 >500 29-30

para-Aramid 340 560 >590 >550 29

Points to be kept in mind while selecting and designing
flame protective clothing:

•The thermal or burning behavior of textile fibers

•The influence of fabric structure and garment shape on the burning

behaviour

•Selection of non-toxic, smoke free flame retardants additives or

finishes

•Design of protective garment depending or its usage with comfort

properties

•The intensity of ignition source

•The oxygen supply

Requirements for flame retardants
Fire retardant properties
• Commence thermal activity before and during the thermal decomposition
of the
Polymer

• Not generate any toxic gases beyond those produced by the degrading
polymer itself

• Not increase the smoke density of the burning polymer

Mechanical properties
• Not significantly alter the mechanical properties of the polymer

• Be easy to incorporate into the host polymer

• Be compatible with the host polymer

• Be easy to extract/remove for recyclability of the polymer

Physical properties
• Be colourless or at least non-discolouring

• Have good light stability

• Be resistant towards ageing and hydrolysis

• Not cause corrosion

Health and Eenvrionmental properties

• Not have harmful health effects

• Not have harmful environmental properties

Commercial viability
• Be commercially available and cost effective
Burning and Flame Retardant
Mechanism:
Flame retardants function by their interaction or interference with one
of the three required components of fire:

• A combustible substance or fuel.

• Heat, supplied either externally or from the combustion process itself.

• An oxidizing gas, primarily oxygen.

1. Dilution:
Reducing the total quantity of combustible material improves overall
flame retardation.

For example; madding fillers, such as clays, to polymer systems

reduces flammability.

In some cases, such as glass fiber reinforced composites, the glass

fiber stiffens the polymer. On exposure to heat or a flame, the glass may
prevent the polymer from melting away from the flame.

In addition, the glass act as a heat sink so that less energy input is
required to ignite the polymer on a second exposure to heat3.
2. Generation of Noncombustible
gas:
Example- calcium carbonate decomposes at 825oC to generate the
solid(calcium oxide), and the gas(carbon dioxide); these products do not
support combustion.

Some materials decompose to produce water vapour as the

noncombustible gas.

Example- Aluminumoxide trihydrate (Al2O3.3H2O) begins to decompose

at 230oC with the release of 34.5 wt% of its original mass as water vapour.

Typically, 50-100 parts by weight of these compounds are required per

100 parts of polymer to achieve flame retardation.
3. Gas-Phase , Free-Radical inhibition:
•On Combustion: hydrocarbons fragments vaporize, react with oxygen and
form free radicals.

•Free radical formation is highly exothermic,

•The process continues unless free-radical formation is interrupted and stable

species are produced.

HO. + CO -> CO2 + H. Highly Exothermic

H.+ O2 -> HO. + O. Chain Branching
O. + HBr -> HO. + Br. Chain Transfer
HO. + HBr -> H2O + Br. Chain Termination

The HBr from the decomposing brominated compound deactivates the free
radicals in the vapor phase.

Chlorinated compounds function in the same manner.

In practice, often twice as much chlorine-containing compound is required as
•Chlorinated compounds function in the same manner.
Generally, twice as much chlorine-containing compound is required as
bromine-containing compound.

•Compounds containing fluorine generally exist as functional polymers

Very stable and decompose only at high temperature.
Hydrofluoric acid when liberated is an effective deactivator.

•Antimony oxide acts as a synergist with halogens, particularly chlorine and

bromine.
Almost ineffective if used without halogen.

Sb 2O 3 + 6HBr 2SbBr 3 + 3H 2O

•Antimony tribromide forms a dense white smoke that snuffs the flame by
excluding oxygen from the front of the flame.
 4. Solid-Phase Char Formation

•Formation of layer of char from from insulating or minimally

combustible material

• reduces volatilization of active fragments and absorbs and dissipates

heat.

•The effectiveness of the flame retardant is specific for each polymer

•For example, phosphorous based flame retardants are effective in

producing minimally combustible char in phenylene oxide-ether
polymers, but are essentially ineffective in styrenic polymers
5.The formation of a glassy
interface on pyrolysis:

•Used mainly for borate-derived finishes

•Deprive the flame of the oxidizable substrate and hinder further

flame propogation.

• Borax/Boric acid is effective on cotton

Categories of flame retardants
Reactive type:
•Added during the polymerisation process
• Become an integral part of the polymer.
• The result is a modified polymer with flame retardant
properties and different molecular structure compared to the
original polymer molecule.
•Are used mainly in thermosets
 
Additive type:
• Incorporated into the polymer prior during or after
polymerisation.
•Not chemically bonded to the polymer.
•Used especially in thermoplastics.
• If they are compatible with the plastic they act as
plasticizers, otherwise they are considered as fillers.
Flame retardents cam also be
classified as:
• Inorganic flame retardants

• Organophosphorus flame retardants

• Nitrogen-based flame retardants

• Halogenated flame retardants

• Barrier technologies i.e intumescent systems

1. Inorganic flame retardants
•Generally are metal hydroxides
•Functionas smoke suppressants.
•Widely used as substitutes tobrominated flame retardants.
•Added as fillers into the polymer
•Considered as immobile

Types of inorganic flame retardents:-

•Aluminium hydroxide
•Magnesium hydroxide
•Ammonium polyphosphate
•Red phosphorus
•Antimony trioxides
•Zinc borate
•Zinc hydroxystannate (ZHS) and Zinc stannate (ZS)
1.Aluminium hydroxide (ATH)
•Available in a variety of particle sizes
•“heat sink” effect
•Due to the dilution of combustible gases by the water formed as a result of
dehydroxylation.
• Alumina formed as a result of thermal degradation of ATH slightly above
200 °C high loading levels

2 Magnesium hydroxide
• Acts, in the same way as ATH,
•Thermally decompose sat slightly higher temperatures around 325 °C.
•Combinations of ATH and magnesiumhydroxide function as very efficient
smoke suppressants in PVC.
 3. Red phosphorus
•Efficient as a flame retardant in oxygen containing polymers such as
polycarbonates, polyethylene terephatalate (PET), polyamide and phenolic
resins.

•Flame retardancy takes place due to formation of phosphorus-oxygenbonds

that reduces the ester linkages into cross linking aromatic structures with
lesservolatility.

Drawbacks:-

•The red colour that could lead to discoloration of polymers

•The formation of toxicphosphine gas during combustion and long term
storage
 
4. Ammonium polyphosphate (APP)
•Used as an acid source in intumescent systems

•Effective in polyamides

5. Antimony trioxide
•Alone does not function as a flame retardant
• But in combination with halogenated flame retardants it functions as a
synergist.
Advantage:
•addition ofantimony trioxide is to reduce the amount of halogenated
flame retardants applied to thepolymer.
6. Zinc borate
• Used mainly in PVC

• Cannot be used alone acts as synergist together with brominated

compounds.

7. Zinc hydroxystannate (ZHS)

and Zinc stannate (ZS)
•Used as alternative non-toxic synergists to Antimony trioxide in PVC
and other halogen-containing polymer systems.

•Acts as fillers
2. Organophosphorus Flame Retardants

•Are primarily phosphate esters

•Manly used for cellulose fibres

Types of Organophosphorus Flame Retardants:-

•Triethyl phosphate

•Aryl phosphates
Triethyl phosphate
•Can be used alone or together with a bromine synergist, such as antimony
trioxide

•Used for unsaturated polyester resins

Aryl phosphates
•Include triphenyl-, isopropyl-, andt-butyl-substitutedtriaryl and cresyl
phosphates.

•Used for phthalate plasticized PVC

3.Nitrogen-based flame retardants
•Inhibit the formation of flammable gases

•Used in polymers containing nitrogen such as polyurethane and

polyamide

•Examples:
melamines and melamine derivatives
 4 .Halogenated flame retardants
•Primarily based on chlorine and bromine

•React with flammable gases to slow or prevent the burning process

•Polybrominateddiphenylethers (PBDEs) form an important class of

halogenated flame retardents

Halogenated flame retardants can be divided into three classes:

• Aromatic, including PBDEs in general and PentaBDE in particular.

• Cycloaliphatic, including hexabromocyclododecane (HBCDD).

• Aliphatic
 5. Barrier technologies
(Intumescent system)
•Involve layers of materials that provide fire resistance.(

Examples-
•boric acid-treated cotton material sused in mattresses , blends of
natural and synthetic fibers used in furniture and mattresses
•high performance synthetic materials used in fire fighter uniforms
and space suits.

Almost all intumescent systems comprise, in general, of three basic

components
• a dehydrating component, such as APP
• a charring component, such as pentaerythritol (PER)
• a gas source, often a nitrogen component such as melamine

The main function of APP is to catalyse the dehydration reaction of

other components in the Intumescent system
Other intumescent systems :

•Expandable graphite and silica-based and metal hydroxide compounds,

incorporated as nanocomposites

•Extended nanoparticles of clay as char-forming fillers for good fire

protection.
Application Techniques:

• Two-bath process
• Suspensions and emulsions:
• Solvent suspensions
• Water-in-oil emulsions
• Oil-in-water Emulsions
• Cellulose-ester process:
 Thermoplastic fibers
Flame retardancy of the synthetic fibers is obtained by

•Mechanically building the retardant with the polymer before it is

drawn into a fiber, or
•Chemically modifying the polymer itself. Incorporation of

•Chemicals in the dope before spinning the fiber fiber has not been
very successful.

•Binders are also used

•Experimental finishes using graft polymerization, in situ

polymerization of phosphorous-containing vinyl monomers or
surface halogenation of the fibers also have been reported.
Flame Retardant (FR) Pet Fibers
through P-N Synergism
A very small amount of the FR chemical could impart fire
resistance of very high order to polyester.
•Acrylamide-grafted-phosphorylated (AM-g-P) PET fibers
containing just 0.189% phosphorus on-weight-of-fiber (owf).

•Methacrylamide-grafted-phosphorylated (MAm-g-P) polyester

fibers at the 0.77% phosphorus content level.

• Efficiency of phosphorus in presence of nitrogen that was

achieved was at 263% for acrylamide (AM) system

•This is attributed to P-N synergism in case of the FR polyester

system when the nitrogen is in the amido form present in AM and
MAm monomers.
Two types of groups of vinyl monomers are used -

• N-deficient,
Aacrylic acid (AA) and Methacrylic acid (MAA), and the other

•N-containing ones like

Acrylonitrile (AN), Acrylamide (AM), and Mthacrylamide (MAm).

The chemical initiation method

Initiator -benzoyl peroxide(0.125%)
On heating,
•The benzoyl peroxide decomposes to give a free radical,
abstracts a H atom from another chain.
• The free radical formed reacts with the monomer molecules to form a chain
on the backbone
•This chain propagates till its termination in the bath at a later stage.
•Thus the graft is incorporated in the poly (ethylene terephthalate) chain
molecule.
Phosphorylation of Grafted Polyester
Fibres
Carried out by treatment of
•phosphorus oxychloride in dry benzene along with

• 2% pyridine as a catalyst in reflux condenser

•for 1 – 6 h at 60 – 110°C.

After completion of the reaction,

•samples refluxed with benzene for 4 h,

•stored in P2O5 desiccators.

Synergistic Influence of Amido Nitrogen in P-N
Bond in FR Polyester Fibers
Moisture Absorption of Grafted-Phosphorylated
Polyester Fibers
Dyeability of Grafted-phosphorylated Polyester
Fibers with Cationic and Acid Dyes
 Flame Retardancy Testing

observations made are:

•The ease with which the material ignites
•The duration of flaming
•The duration of afterglow
•The extent of burning and length of char
•The duration of flaming and smoldering
•Assessment of detectable amounts of smoke
Various flame Retardant Testings

•The Federal test

•Test 16 CFR 1610
•16 CFR 1615/1616
•The National Firefighters Protection Association (NFPA)
• ASTM D2863-00
• The Room Corner Item Test (ISO 9705)
• The Cone Calorimeter Test (ISO 5660)
• LIFT apparatus test (ISO 5658)
•UL 94 of underwriters laboratory
• Fire resistance
• Flammability:
 Toxicology
•Of greatest concern are those with halogens attached to the
carbon backbone, particularly the halogens: chlorine and
bromine.

Brominated flame retardants (BFRs), are widely used

• cost effective means
•durability
•performance of the material.
•Three most commonly used BFs are penta-, octa- and Deca-
brominated diphenyl ethers.
• Collectively they are referred to as polybrominateddiphenyl
ethers, or PBDEs

Chlorinated flame retardants (CFRs ) are used in textiles,

paints and coatings, plastics and insulation foams.

• chlorine containing flame retardants persist in the

environment and may accumulate in the tissues of humans
and other animals.
• BFRs are very stable-they do not break down easily in the
environment

• Attach to particles and accumulate in media such as dust and

sediments.

•BFRs also are light enough and are transported long distances through
the atmosphere.

•Chemicals are readily absorbed by the body where they accumulate in

fatty tissues.

•BFRs disrupt thyroid function , causing hyperactivity and problems

with learning and memory.