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By : Raghav Mehra Mtech 1st year
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
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.
The combustion leads to a production of heat that is spread out (delta H1) 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) FIRE Air (oxygen) Ignition source Fuel No Fire: when any one side is missing Fuel Ignition source .
transport. electronic. etc the use of organic polymers is restricted because of their flammability .Why use of Flame Retardants ? In most cases polymers initiate or propagate fires because. being organic compounds. building. In many fields such as electrical. they decompose to volatile combustible products when they are exposed to heat.
Reduce smoke emission. Avoid dripping . In order to lower the "fire risk" and the "fire hazard³ of these synthetic polymers. flame retardants need to be added into the polymer.Use of synthetic polymers has greatly increased. The role of these additives is to : Slow down polymer combustion and degradation (fire extinction).
the flash over : Control fire properties of combustible items.e. Provide for suppression of the fire.Fire Dynamics The goals for fire retardant can be simply stated in the following items 1. Flash over time vs fire retardant use . Prevent the fire or retard its growth and spread i.
Protect occupant from the fire effects : Provide timely notification of the emergency. Smoke release vs fire spread .2. Provide areas of refuge where necessary and possible. Protect escape routes.
Minimize the impact of fire: Provide separation by tenant. control. communication. Provide for continued operation of shared properties. occupancy. Provide reliable communication with areas of refuge. Provide for fire department access.3. and selection. or maximum area. Maintain the structural integrity of property. 4. . Support fire service operations: Provide for identification of fire location.
. To increase the escape time of persons.5.
more flammable is the fiber .transition temperature (Tp) pyrolysis temperature and (Tc) the onset of flaming combustion Lower the Tc (and usually Tp) and hotter the flame.glass transition temperature Tm .Burning of fibers The burning behavior of the fibers depends on / determined by a number of thermal transition temperatures and thermodynamic parameters Tg .
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.8% O2). Fibers that have a LOI values of 21 or below ignite easily and burn rapidly in air (20.Limiting Oxygen Index (LOI) LOI (limiting oxygen index) measures the inherent burning character of the material. . LOI values above 21 ignite and burn more slowly.
2 Polypropylene Modacrylic PVC meta-Aramid para-Aramid -20 <80 <80 275 340 165 >180 >180 375 560 550 450 450 >500 >550 18.9 20-21.5 20-21 18.LOI values of different fibers Fiber Tg (soften) oC Tm (melt) oC Tp (pyrolysis) oC Tc (ignition) oC LOI (%) Wool Cotton Viscose Nylon 6 Nylon 6.6 37-39 37-39 29-30 29 .4 18.5 20-21.6 Polyester Acrylic 50 50 80-90 100 215 265 255 >220 245 350 350 431 403 420-447 290 (with decomposition) 470 >180 >180 410 >590 570-600 350 420 450 530 480 >250 25 18.
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 .
primarily oxygen.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. supplied either externally or from the combustion process itself. An oxidizing gas. Heat. .
On exposure to heat or a flame. Dilution: Reducing the total quantity of combustible material improves overall flame retardation. For example. In some cases.1. to polymer systems reduces flammability. such as clays. In addition. the glass fiber stiffens the polymer. . such as glass fiber reinforced composites. madding fillers. the glass act as a heat sink so that less energy input is required to ignite the polymer on a second exposure to heat3. the glass may prevent the polymer from melting away from the flame.
3H2O) begins to decompose at 230oC with the release of 34. these products do not support combustion. . Typically.5 wt% of its original mass as water vapour. Generation of Noncombustible gas: Example.calcium carbonate decomposes at 825oC to generate the solid(calcium oxide). to produce water vapour as the Example.Aluminumoxide trihydrate (Al2O3.2. and the gas(carbon dioxide). 50-100 parts by weight of these compounds are required per 100 parts of polymer to achieve flame retardation. Some materials decompose noncombustible gas.
Free-Radical inhibition: On Combustion: hydrocarbons fragments vaporize. Chlorinated compounds function in the same manner. Chain Transfer HO. + HBr -> H2O + Br. Free radical formation is highly exothermic. The process continues unless free-radical formation is interrupted and stable species are produced. Chain Branching O.3. + CO -> CO2 + H. + Br. Highly Exothermic H.+ O2 -> HO. + HBr -> HO. react with oxygen and form free radicals. In practice. often twice as much chlorine-containing compound is required as bromine-containing compound. Gas-Phase . Chain Termination The HBr from the decomposing brominated compound deactivates the free radicals in the vapor phase. HO. . + O.
twice as much chlorine-containing compound is required as brominecontaining compound. Hydrofluoric acid when liberated is an effective deactivator. Compounds containing fluorine generally exist as functional polymers Very stable and decompose only at high temperature. particularly chlorine and bromine. Sb 2 O 3 + 6HBr 2SbBr 3 + 3H2 O Antimony tribromide forms a dense white smoke that snuffs the flame by excluding oxygen from the front of the flame. . Antimony oxide acts as a synergist with halogens. Almost ineffective if used without halogen.Chlorinated compounds function in the same manner. Generally.
4. 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 . 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.
5. Borax/Boric acid is effective on cotton .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.
Categories of flame retardants Reactive type: Added during the polymerisation process Become an integral part of the polymer. Used especially in thermoplastics. otherwise they are considered as fillers. . The result is a modified polymer with flame retardant properties and different molecular structure compared to the original polymer molecule. If they are compatible with the plastic they act as plasticizers. Are used mainly in thermosets Additive type: Incorporated into the polymer prior during or after polymerisation. Not chemically bonded to the polymer.
e intumescent systems .Flame retardents cam also be classified as: Inorganic flame retardants Organophosphorus flame retardants Nitrogen-based flame retardants Halogenated flame retardants Barrier technologies i.
Widely used as substitutes tobrominated flame retardants.1. Inorganic flame retardants Generally are metal hydroxides Functionas smoke suppressants. 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. Thermally decompose sat slightly higher temperatures around 325 °C. Alumina formed as a result of thermal degradation of ATH slightly above 200 °C high loading levels 2 Magnesium hydroxide Acts. Combinations of ATH and magnesiumhydroxide function as very efficient smoke suppressants in PVC. . in the same way as ATH.Aluminium hydroxide (ATH) Available in a variety of particle sizes ³heat sink´ effect Due to the dilution of combustible gases by the water formed as a result of dehydroxylation.
polyamide and phenolic resins.3. Drawbacks:The red colour that could lead to discoloration of polymers The formation of toxicphosphine gas during combustion and long term storage . Flame retardancy takes place due to formation of phosphorus-oxygenbonds that reduces the ester linkages into cross linking aromatic structures with lesservolatility. polyethylene terephatalate (PET). Red phosphorus Efficient as a flame retardant in oxygen containing polymers such as polycarbonates.
4. Antimony trioxide Alone does not function as a flame retardant But in combination with halogenated flame retardants it functions as a synergist. Ammonium polyphosphate (APP) Used as an acid source in intumescent systems Effective in polyamides 5. Advantage: addition ofantimony trioxide is to reduce the amount of halogenated flame retardants applied to thepolymer. .
6. Zinc hydroxystannate (ZHS) and Zinc stannate (ZS) Used as alternative non-toxic synergists to Antimony trioxide in PVC and other halogen-containing polymer systems. as synergist together with brominated 7. Zinc borate Used mainly in PVC Cannot be used alone acts compounds. Acts as fillers .
Organophosphorus Flame Retardants Are primarily phosphate esters Manly used for cellulose fibres Types of Organophosphorus Flame Retardants:Triethyl phosphate Aryl phosphates .2.
isopropyl-. such as antimony trioxide Used for unsaturated polyester resins Aryl phosphates Include triphenyl-. andt-butyl-substitutedtriaryl and cresyl phosphates.Triethyl phosphate Can be used alone or together with a bromine synergist. Used for phthalate plasticized PVC .
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 .3.
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. including hexabromocyclododecane (HBCDD). Aliphatic . Cycloaliphatic.4 .
of three basic components a dehydrating component. such as pentaerythritol (PER) a gas source. such as APP a charring component. blends of natural and synthetic fibers used in furniture and mattresses high performance synthetic materials used in fire fighter uniforms and space suits. 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 .( Examplesboric acid-treated cotton material sused in mattresses . in general. Barrier technologies (Intumescent system) Involve layers of materials that provide fire resistance.5. Almost all intumescent systems comprise.
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. Binders are also used Experimental finishes using graft polymerization. Incorporation of Chemicals in the dope before spinning the fiber fiber has not been very successful. . in situ polymerization of phosphorous-containing vinyl monomers or surface halogenation of the fibers also have been reported. or Chemically modifying the polymer itself.
Acrylamide-grafted-phosphorylated (AM-g-P) PET fibers containing just 0.189% phosphorus on-weight-of-fiber (owf). Methacrylamide-grafted-phosphorylated (MAm-g-P) fibers at the 0. polyester 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.77% phosphorus content level.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. .
Aacrylic acid (AA) and Methacrylic acid (MAA). abstracts a H atom from another chain. and Mthacrylamide (MAm). 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. .125%) On heating. The benzoyl peroxide decomposes to give a free radical. Thus the graft is incorporated in the poly (ethylene terephthalate) chain molecule. and the other N-containing ones like Acrylonitrile (AN). The chemical initiation method Initiator -benzoyl peroxide(0.Two types of groups of vinyl monomers are used N-deficient. Acrylamide (AM).
stored in P2O5 desiccators. .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.
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. Collectively they are referred to as polybrominateddiphenyl ethers.and Decabrominated diphenyl ethers. octa. or PBDEs Chlorinated flame retardants (CFRs ) are used in textiles. plastics and insulation foams. chlorine containing flame retardants persist in the environment and may accumulate in the tissues of humans and other animals. . particularly the halogens: chlorine and bromine. Three most commonly used BFs are penta-. Brominated flame retardants (BFRs). are widely used cost effective means durability performance of the material. paints and coatings.
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. 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.