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    Material Flamability, Combustion, Toxicity and Fire Hazard in Transportation

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    Vlad Kubinyecz

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    © All Rights Reserved
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    ‘Aallable online at wonusciencediectcom corence Gornecrs PROGRESS IN ENERGY AND COMBUSTION scENCE PERGAMON ‘Progress in Energy and Combustion Selsnce 29 (2008) 247-299 wor lever commoctepees Material flammability, combustion, toxicity and fire hazard in transportation Indrek 8. Wichman* Deparment of Mecharical Ergtnzring Michign State Univers, Bat Lansing, ME 48824226 USA Received 30 October 2001; aseopied 4 March 2008, Abstract ‘Maay materials wsed in transportation vehicles are combustible, often dramatically so. These materials may include gases, liquids end solids. They are sometimes employed in order to increas fuel efficiency, reduce manufacturing cost or meet other ‘market demands such as durability or appearance. Ftensive research has been conducted on such mtetias both with and ‘without the expressed intent of applying the resus direetly to vansportation. Combustion and fire research, considered generally, are much broader than (and in fact encompass), tbe specific applications to transportation issues discussed here, Much if not most of fir and combustion researc, therefose, has a dizect bearing on ‘cansportation. This review ties together disparate subjects of fundamental fie and combustion resexcch tht have relevance to transportation fire. The goal is w provide a technical overview of the combustion literature related to, but not exclusively ‘concemed with or focused on, transportation fire safety ‘Although they are mot large pereeatage of tansportation-elated fatalities, Gres can be costly in human and economic rms, Inthe United Stztes, pst-colision fires occur in 15% of fatal motor vehicle accidents, while approximately 20% of air traffic fatalities are areihate to fire. This zeview adresses scientific and technical engineering issues i the les offre inition; re spread: products of combustion and their toxicity; and practical fire prevention in vehicles and other modes of tansportation ‘© 2008 Elsevier Ltd, All rights reserved. Keyword: Maseil Ramabiliy; Combustion; Transpaation Contents T. Tntoduction «26s eeeecees cae cece 288 LL. Fie safery : eae 288 Aad Fee initiafon 20202222 02000200. eae zs0) LIZ Fire grown Se : fee 251 A.L3. Fire chemisuy 0200... 7 ant wi 251 AIS Summary... oer He 254 12. Discussion ‘| 231 2. Fire ination. ae ‘| 252 Spec eae 2 282 DLE Gases.. : : i 252 212. Liquids ete Steen sree ess 213. Solids 22. * : : 255 22, Flammability and ignition... Sete eet eeeeee te ose 221. endef Sanszbiy tod gion a cap) 257 22.2. Flammability and ignition lteramre review... e000. 258 Corespondiag author. Te: + 1-517-555-5131; fa: + 1-817-353-1750, Evra address: wishnan @egransacd (LS. Wichias), 1360-12853) ~ soe Som manse © 2003 Elsevier Le. All ght essed. ei 10 1016'90360-1285(05)00027-3 8 15. Wickman / Progress in Energy and Combustion Science 29 2008) 247-209 2.3, Rate of hea release (RHR): the cone calorimeter and other diagnostic devices 260 23.1. Background and principles of the cone calorimeter 260 23. Practical uses of the cone talarimeter and other fie diagnostic devices. 263 3. Hie spread, 265 3.1. Fire spreag over liquid fuels : 265 3.2. Theory of fire spread over liquid and solid fuels... 2... = 287 33. Fire and tame spread over materials : 269 4. Fire chemistry ; : fie 2 4.1. Prodvets of thermal decomposition and combustion : 273 4.1.1. A cas study: the sunshine mine : 216 42. Toxciy. i 207 42.1. PVC and Sre-g3s toxicity 280 42.2, Polymer decomposition and toxicity 281 423. PU foam toxicity _ : 2 282 424, Toxicity of ire retarded materials; toxicity of foams and fabrics; influences of heating rates on tonicicy -. : 283 43, Smoke and retardants 284 5. Vehicle fies. 236 5.1, Buses : 286 Railway and subway ears 286 53. Aircraft eabins. .. 287 S. Motac vehicles. 288 6. Conetusions 291 Acknowledgements 292 References 22 1. Introduetion tation fre and materials flammability. OF the move than In the past, the vehicles used for wansporttion were constructed almost exclsively of wood and metal. The general fire behavior ofthese materials, for example whether ‘or mot they readily bum, was common knowledge, and alterative materials were limited both ia their availabilisy and in their vse, ‘With time and technological sdvancement, larger numn- bers of potentially combustible materials have been used in transportation vehicles. The precise reasons ate many, although ewe prominent design considerations have been (1) atass reduction, resulting in ineeased fel efiiency, 20d @) reduced manufacturing costs. Numerous complicoed physical processes occur uring the combustion of materials Trequently used in Cansportaton: these include, but sre not Jimited to dripping and canning of liquefied surface layer ring burning; by-product of combustion loss of material integrity and desirable physical performance properties; production of lightweight, combustible, decomposition ses: and fame spread nearby combustible materials. ‘This review was prepared in accordance with an agreement between General Motors (OM) and the US Department of Transportation, Tae document outlining this research agreement is described in the setiement agreement between the United States Department of Transportation and the General Motors Corporation daved March 7, 1995, Pat of the research program established by this agreement required a iterature search of stcles related to Canspor- 1000 anicles culled from research journals by GM engineers, approximately 150 were sbstacted at Michigan State Univesity (MSU). To avoid eopytiaht infingemen, ‘copyrighted abstracts were not incindet in the Transpor: tation Fire Salery CEFS) Bibliography developed by Laue {1}, Original abstracts for the approsacy 150 selected arses were writen by me and included in the GM TES ibliogaply. The present arile is, in pa, ¢ topically crganized and condensed version of these sbstacted icles, Nevertheless, in addition 1 the works abstracted in the TFS bibliogaphy, numerous additional works ere described snd discussed when tty shed light on the parcular subjects discussed, These additions were cariod ‘out my disceton without sgnfieant input from GM. “The intent inthis review is i provide a systematic examination of te combustion, fammabilty and wxiciey feawes of materials associated with transperation and ceasporstion fies. The eade is asomed to have suicont scientific or engineering background to understand the teehaieat content of this zeview, The background discus sons fou in each subsection are meant o outing zelevant fundemontal concepts and methods in ach research fel. Bu. Fire safety ‘Three means are employed for addressing the problem of fie safety in vobicles and over modes of transportation, 118, Wickman / Progress Energy and Combustion Science 29 (2003) 247-299 29 Nomenclature PB 2 ? nemo Sane EO nese fae Subseripts Bowne Greek symbols An Ae Pctronsntl ft (nol) specitic heat per unit mass (of 8s) (eink) specific hear per unit mass (of solid) (em) concentration of species i (mma¥/L?) activation energy (eémol) hat loss coefvient (el? ¢ K) rate constant, k= Rexp(—EiRD) camo’) eH) saterial thickness (L) istance from flame tp to fel surace (L) ‘ass flux of fuel fom surface of deem: posing fuel (iL?) -mass fx at ignition (m/L 1) deat ux (/L* 1) Ineatng rate (et) universal gas constat (efmol K) surface ares (L?) ignition time ( flame temperacure (K) ignition temperature (K) suface gasifeaton or ‘vaporizasion’tem- perature (K) ambizat temperature (K) veiocity Li) velocity of lame spread (Lit) velocity of gas flow (LA) volume (L*) ‘width of material (L) flame tip position (in wind-aided fame spread) (L) pyrolysis front postion (wind-sed flame spread) (L) owidizer mass fraction combustion ‘lame gas st ignition oxidizer soba ambient ‘ermal diffusivity, a= Ape, iA) heted segment of solid fuel ia the plane of flame vel (2) enthalpy difference (ohn) enthalpy of combustion perunitmess (en) aH de m ° Acronyms ‘ABS. AFB AIF ASTM BART ce cD Gc-Ms cM HC HCL HCN HDPE HR HR Hvac ABS or impPS m 180 LDPE Lov LEE Lor LF MAR N NBS enthalpy of combustion pecmole (eal) gs phase thermal conductivity (Lt K) solid phase thermal conductivity (elt) density G/L?) acrylonitilo—butadiene styrene ammonium peataborate tomatic tansmission uid American Society for ‘Testing and Materials Bay Arca Rapid Transit Systems cement block computational fluid dynamics cyanide chloroparafins ‘cabin ator spray system ret inlet mass spectrometry dimethyl phosphate Deparment of Transportation ‘iflerental scanning calorimetry T,, The intersections defined by the focations T;, T, are the stationary solutions of Ea. (2.1) Yue eal ease in which sesstnt depletion Snaly diminishes the eneraion erm isnot examined here. The extension canbe ound in the ere (13 1S, Wickman / Progress in Energy and Combustion Science 29 (2008) 247-299 288 0 ts Sean niriear te Fig Temporal plot of toaperatur ins combustion calarietr, The ignition an extinction pot ce nticatd The level ste igaition is predvced by reactant depletion (whieh i ticle i the Snpliied preseataton even et. were aTiGe— 0. Point 2 is unstable whereas pint 1 is Sable, mening ia mall pertron ofthe aon for Fae point 1 rete to tat point. The division between wast explosive and posihly domexploive behavior fess for carve (2) AL hs socalled ical” condton iris esily show that he Semenov number Seis given by eon be emia ate of teat release) 5 * te of heat loss to suroundings) = (AM CHRER VD an ARTES * bape eh Whoo Se < Ie, the mixture is it regime (1), explosive; when Se> Ve, the mistae is in regime (3), which is potentially non-explosive between points 1 ané 2 (bounded by T; and 7). Sei Ue ratio of host generation rate to heat Joss rate, so.a physical interpretation of the criterion Se = eis possible. Se is increased by inoreasing SIV = of all, ‘common geometric shapes the sphere has the largest value of SIV. Iki increased by increasing the beat los coeliceat ‘h, and by decreasing the chemical reaction rite (iy ‘eressing # or iacreasing E, ot both) [cis also possible to examine the diffesntial equation in order to determine the time io ignition, ig, When ignition is approached, the generation of heat by chemical reaction ‘exceeds the heat fostes, The continual thermal energy feedhnack produces a sharp rise in the beating rate, or rte of temperature Increase. Cousequendy, in te lowest appcoxi- ‘mation the ime to ignition is determined as the time at which dhe T(@ vs. ¢ slope becomes inflate The result is post RTBIED po : a Rea Re Be es which provides the paramesic proporionaites for zas- ‘hase ignition of combustible mixtures. The dependence pon all paraieters exoopt Zand J 18 algebraic, and therefore not highly ceaitive, teres the dependeace nF anid T, is exponential, and therefore extremely seniive The primary fanouoa of wspar, for example, ie toaise the local temperse, thereby decreasing eaponeataly the tie to ‘gaiion. For example, with ~ 30 kealfmat = 126 Wimol ‘re see tha ncreasiag 7 ffom $00 o 1000 K decreases the ‘ignition time by the factor e™ = 3x 10~', whereas iterescing Ty from 1000 to 1200 K decreases it by &-** 8x 10°?) ‘Conssquently the igaiion of combutble gas mixture canbe understood 3 4 balance betweea heat generation BY chemical esction and beat loss by concuction, convertion, sd fadation. The voltme of gos to be igoited mast be sufficiently tage (with characteristic linear dimeasion approximately comparable 10 fame ‘hickaess (11), te ‘gal troperetare must be suiently high (greater than equal to Tn Fig 2), av reactant depletion cannot be an important limitation in the early stage of ignition. These ennecpi are useful for understating isnon of fame over liquid and solid fuels, since ignition nearly always occurs in the gas Several Limitations cload this Afealired picture of ignition. One of these is th the beated gas volume V caust be approximately at least 8 Wide a5 the characteristic flame thikness during combustion. Ifthe hewed volune is Qo Qs Fig. 2 Iealize plot of Oye tt 2p, versus temperate Reactant depletion sneered ele the dimissnnent of C} would cause Qa decrease, Joveling aff shoul! also occur (withour esetnt depletion) 3b 7-0 Since exp —E/RT) spproaces unity in ch Tania. Ts "Wvelngoff region canbe considered as being co he right (onthe graph) ofthe gion show. When S¢ ch tony one point. Curves resembling “Tare alias explosive, whereas curs ceverbling "are now stplosive smaller, the heat loses the surroundings ate large enough to self quench the incipient reaction, regardless o£ magera- tue [3,10,11, pp. 268271). Another Himitation is that real ‘g88e5 undergo thermal expansion when they are heated ‘Therefore the volume of gas being heated changes during beating unless ignition oecurs in a constant volume bomb calorimeter, The constat volume bomb calorimeter, sed in practice 10 measure the heat release of various fuels in oxidizing envisonments, 18 & commonly used ignition device, whose operation Is described in Ref. {14} sand whose uses in ASTM esting are lsted.? Another rmecans of ignition keeps pressure, not volume, constant, so the gas volume changes during heating, It is dificult to conduct systematic ignition experiments because © hany ASYD wit use ths bom calorimeter, From the ASTM website (Wan ong) £09 finds the following fs related to Uuansportation, D4809-95 (Heat of Combustion of Lighid Hydrocarbon Ful: D-4868-90 Het of Combustion of Burner! Diesel Fools); 6246-99 (Not Host of Combustion Specific Exeryy—ot Avintion Foels 6277-99 (Standard Speciation for Gre 82 Unleado Avion Gesolne); D6202-008 (Evaluation of Autonet Engine Oils onthe Fuel Beonomy of Passenger Cas and Light Dary Trucks in VIA Spa lgmtion Engise; DSS62-995 (Evaluation of Engine Oils in TworStrake Cycle Torbo- Supercharged 6V92TA Diesel Engine). te cues fx Ong a0 Qa the buovancy-indueed flow caused by the rising heated gases adds Quid-dynamic complexity to ignition. ‘Thermal expansion and beoyancy introduce flows that are dificult physically to quantify and expesimenally to reproduce. For ‘his eason, many gas ignition measurements are conducted in the constant-volume bomb calorimeter. These dta ae of Timid value, however, boeause fre initiation generally foccars at constant pressure, not constant volume, Other complications include exosstlows, conceatation gradients, rult-stage ignition [15], osilatry ignition, heat losses to non-simpie neasby surfacos, gas mixtures containing ppariculates, and additional processes too sumerows (0 ‘mention in this review. The interested reader may consult books and articles and symposia proceedings devoted to the subject of ignition * Tithe initation of fire over liquid and soli fuels, inition into fame occurs in the gas, The condensed phase must be gnsified t0 produce a combastible gaseous mixture of Fel vapor and oxidant (st), sually above or near the gosifving ‘condensed material, The mass Now rate of vole produets See, €@, volumes ofthe Combustion Symposia (aterotiona) fn which ‘whole srons are devted to ignition in somerous peice problems. Also, the Fire Safty Seieare Provsdings oni discussions of igi Tevant 0 fs. 1S, Wickman /Progrse in Energy and Combuaton Science 29 2003} 247-209 255 cf condensed phase pyrolysis or gasification rust, in ener, be sufficient 19 produce what may simplistcally refered to asthe lower flammable limit of the fueVoxiizer mixta. This mixture can be ignited by an external (pilot) source. Numerous complications arise, however. Among, these ar spatially inhomogencoms temperatures and reac~ teat concentrations, heat losses from gas tp conlensed ‘phase, flows in both phases, infuences of buoyancy. For all of these real-world reasons, the ‘lower flammability Timi? refered to previously is usually an unmet and unrealized Idealization, and as such is unable to properly characterize the actual condition of the gas at ignition. Ia other words, it is not the flammability of the mixture itself, rather itis a combination of conditions met by the mixture and the surroundings that permits ignition to oceur. Self-ignition is generally not relevant to many applications in fire. PHoted ignition texts are more common [16,17]. In such ignition ‘9st, small ‘pit’ flame s placed ator near the condensed phase sarface (where the fuel vapor and as are most neszly ‘well mixed) fora fxed time interval, then it is withdraorn, Ignition oceurs whea combustion is sustained without the pilot flame. 2.1.2, Liquids Tn order to ‘ignite 2 Tiguid fuel,’ the liquid =mast be sufficiently heated for a fammable fuel vapooair mixture 10 orm above the lguid phase, As for pure gases, two limits of flammability or ignitabilty are employed. These Emits are the Team limit (whete the vapor-phase mixture is fuel-lean) ‘and the rich limit where the vapor-phase mixture is fuel- rich). Sustained ignition, ox ming, is stained when the fuel production rate from the vaporizing lige fuel can ‘generate 8 lame whose heat release rave i large enough to ‘overcome heat losses (othe liquid. the ambient gas and any nearby walls or surfaces. Thee common measures of Liquid fuel flammability form che tases for Squid flammability tests, These are the closed-cup flash poiet, the open-cap fash point and the theoretical fash point. The closed -cup ‘flashpoint, which is measured ina closed, uniformly heated ‘vessel isthe temperature at which the ¥apoc pressuce ofthe guid fel rises tothe lower Timi of fammabilty ofthe fuel ‘vapor in sir (or other oxidizes). The jlash point isthe fuek liquid surface cemperste at which the fue vapor above the liquid will ignite ito flame in the preveace of a pilot ume. In the open-cap flash point test the vessel is open to the ambient atmosphere. ‘The closed cup flash point test overlooks the important role of concentration and temperature gradients inthe gas mixture and possibly the liquid fael. I is # homogeneous measure, which provides thermodynamic ignitabilicy ‘tteroa ideally independent ofthe actual surroundings. ‘The open-cup flash point test accounts for gas phase gradients of concentration. These can be altered by buoy- ‘ancy (natural convection) and forced convection, a well as the consituesis of the prevailing gas mixture (air, diluted ais, oxygen, ..) Ifthe pilor fame is very mall, ignition can depend upon pilot location, whether too fer from the surface {or significant difusion of fuel or to0 close to the surface (ie. Within the fame quenching distance). Tae optimum pit location may differ for each fuel, for it may depend, ‘upon fuel density, specific heat and conductivity and other ‘properties, Addionally, ignition depends upon th liquid uel in-depth temperature, not merely on the (higher) temperature of the heated surface layer. Consequently, inhomogeneity snd ransient evolution may alter igntability Si the Gash point test (16,17) 24.3, Solide ‘To deseribe the fammability of specific combustible :matecials in the simplest possible burning configuration (the burning slab) one attempes to answer the question “How does the heated surface ignite into fame?” Four expla- ations have been Put fort. Two are based on attainment of ‘2 crscal surface temperature or a minimum volatile 38s fluc inio tho adjacent gas. The remaining two explanations require a minimum oxygen concentration and a miniroum. extort beat Qu. Complications arise because thos four cniteria are closely related and may depend upon other, external variables. The surface temperature and mast fax depend on the oxygen msss fraction and heat ux, xsl the surface mass ux may be a function of the’ surface temporature, and the influence of the air velocity and velocity eld may need to be quantified. The flow field is ‘one ofthe ‘extera!” factors whose influence is dgfeult 10 ‘quantify. Tae incident best flux is the most primitive flammability ‘property. The practical measure of interest is the time to ignition. Most tests specify the oxygen concenteation and the “applied” heat flux Heated gaseous fuels and warm air, mixed to the comrect proportions, can sel-ignit, In many fres thermal radiation fom neaiby fines, or a nearby Layer of hot product gases, or hot walls in close proximipy 10 the surface are the primary reasons why as-yer-unbumed materials ignite into flame. This ignition may be spontaneous (Self-gnition) or piloted. The most rigorous test of Gammability exposes the heated sample to a pilot fame, The two Isnds of pilot flames are continuous and intermitent. Unless a gas ow is present, the continuous, pilot may alter the energetics of the Maramability test, bathing the sample in an additional stream of Beat. Hence, the intermittent pilot is offen prefered. The intermittency interval should be @ mere fraction of ehe charsctristic sample heat-up time, which is measured asthe quotient of the square of the samplo thickness snd its thermal iMRI, Noatag * Ef, c= Alpe, In the “eit as the interaiseney level approaches the sample beat-up time there really is no intermittency and heating 4 in fact, comtinibus. Since a Imowledge of the inftuences of the het flux is crucial, the conditions at the rear of the heated. sample ig. 3) are imporant, because the overall energy balance cau be influenced by this region, Ifthe sample is hick", the conditions at the rear face 0 not influence 256 11S, Wilma / Progress in Breray’ nd Combustion Sconce 29 2008) 247-299 Pilot Flame ‘Test Material lr —N, sonnei genannten q’ou=0? Fig 3 ote ignition of «combustible sli sabjecred ro est x . Ta Inston of te pilot may alter ignition. The thiness ofthe slid say be important if hear losses eccr rom the bace burning. If, howevec, the sample is ‘thin’, the conditions a the rear face of the sample must be carefully contolied, Here, thick and thin mean “thermally thick’ and “thermally thin’, A matetal is themmally thick if, during the course of the entire flammability test, its rear face does not detect the thermal ineut received at its front face, Ie is thermally thin when the thermal response of the front and rear faces ‘occurs simultaneously Experimental data are always interpreted through theoretical explanation. Consider Mikkola and Wiehman [18] and Atveya and Abu-Zaid [19], ia which an explanation. 4s provided for the differonces in the dependence of the ‘ntical incident heat flux for thermally thick and thin materials. For incident heat duxes below the critical heat ffox, the heated surface will not undergo piloted ignition even ifthe surface is indefinitely beated. Above the critical heat Mux, piloted ignition is possible. The explazation of Mikkola and Wickman [18] rested on the formulation of a simple model which consiss essentially of an energy ‘equation in the heated solid integrated over the heated volume, Thus, we have t= Alig — Tail en) for piloted ignition ofa thin sample of thickness | and ig = Teahlg — TaD 25) for piloted ignition ofa thick sample. Here, isthe time to ‘ignition of the material, which is sobjected over this ime period to the net heat lux ¢". Eqs. (2.8) and (2.8) do not explicitly contain heat losses, which ate therefore included in @. The solid density,’ specific heat and thermal conductivity are py, ey, Ay, respectively. The ambient tempersture of the suroundings is Ti and Ti, denotes the temperature of the solid at the moment of ignition. Experimental data plotted in this manner fall accurately onto sraight lines confirming both the qualitative and quantiat- sve accuracy ofthe theory. The ertical eat flux is obtained by the extrapolation of dase Hines tog = ©, a6 shown in Fig. 4a and b, The extrapolation tof = 0° is not permitted by this simple model, however. A more detailed examin- ation ofthis Himit is fou in Ref. (19), which demonstrates the inaccuracy ofthe exrapolation while explaining limiting Gq) ignition heat Buxes in teams of coavective gas ‘ow. The lites showe inthe figures actually curve nea the poiat fg =o, where the corelations of Eqs. (2.4) and (2.5) break down, ‘We note from Eqs. (2-4) and (2.5) that the equations relate ignition tine, exterusl heat flox and atainment of ccitcal surface temperature. If inaddition othe fuel surfece: (1) tee narrow nearby gue region is algo heated to Ti: (2) the concentration of the constituents (eluding the gaseous oxidizer) renders this heated layer of gas igntable and combustible; sod (3) the mass gasification rate is suiciently high, then a colr-sustaining flare may be produced over the heated, pyrclyzing, combustible surface, Traasition from ‘ignition foaming will then occur, resulting in fie initiation, 2.2, Flammability and ignition Tn this section we frst describe basic features of ‘Bammavilty and ignition of real materials by desesbing complicated, real exemple of igaitio in Section 2.2.1. Then in ection 2.2.2 we discuss the TFS Bibliography references on fimnmabiity nd ignitioo. 1, Wickman /Progrezs in Enargy (@) Theemally Thin i (eee) Z er r and Combusin Science 28 (2008) 247-239 27 () Thenally Thicke LZ Yan a (oe?) ig. Plots of versus infact) and ¥ (hick Fuk), showing he near Linea dependence as predicted by the inition easton. ‘As 10, th prodictons trek dowt, esd mechensns that have bea neglected become important eee pie ee Pee ee ta sea cou ee ae eee eae Se ee Hiren eleenear oat enetd ren Cee pan nec cea eee are oy atac es docias tua Mego ees eee eee feed Gaerne see a See case re cee De ee Sooo prepare trarpeel Se ere rer ees oe ee oe Feapfergramnrinpap lia alee Se oe Se Sapa aceon cae ee ee mca ie eee fae et aia ee ee eee ee cs fo cnet cae cea ncaa ees eae aaa the (empirical ignition xe tbe begining of Section 2.13. oder to establish ideas, we preseally examine the story, fom inception of heating to ignition,’ of head rod cakcas shown ia Fig. 5 (AW). Tn he inal beating age the fel sesponds as predicted by neat conduction analysis. The temperate se or de thermally thick sample shows a? tame dependence. Near to but preceding the ignition time, feshes of uosustined flaming ocr in beth the vertical and horizontal sample configurations. When the extemal beat fix islow (y' ~ 0 (0.1 kWin), 2 sucent elapse of ime occurs bewicen ashes for the sample surface «9 therlly ‘qulibrate with the exceroally applied radiant ux. Between fleshes the surface temperature resumes its previous sueootni, steady increase, The surface temperate at the commencomest of sustained flaming i lower than the ‘mornentary maximum fash teaperatre. The flashes occur ‘cause the pyrolsis ofthe sample produces combustible {uel vapors of insutcient quantity fr sustained, cominuons buming. In addition, because the sortce temperature is lover than required or fall boring. Beat losses 19 the susface from the flashes preveat ststsined ignition from being achieved dating the fahes, From Fig. 5 we see hat sustained flaming occurs when the surface temperature produced by extemal heating 80s to a critical value of approximately 650K. As observed by AW: "The conti. ‘ations ofthe gas phase exothemicity mest note ineloded in the determination of this erica! value (of He sutace temperate), Furthermore, th total het conebation othe soli Grom the) Mashes (which i progertional to the area (AW) that were outlined at aaroya [5 and Wichmas [2 focused on celosi se bu rmaay noacellosies—shict we also peimmedc louectain HC ‘ucb—stow the same pater of bebavicr. Sustained Resins by piloted ention occare when surface emperanures xe of the ner TOOK and deviations ae usualy not more than 10-20%, See the cna in Append F of Ret (9 258 18, Wickman / Progress in Energy and Comston Sconce 29 (2003) 247-208 1 f = i ig 5, Surface temperature vers tne hisory for a sample ofr osk sujced 0g 1, = 372°C = 645 K, eventhough temperatres at flashes exceed 7, ‘under the peaks) is small compared to that (irom the extemal flux). Thus, it may be concluded that although the heat lost bby the flame to the solid at the instant of igaition is significant (and may cause thermal quenching, resaltng ina flash) its contribution to the enthalpy rise of the solid is negligible and, consequently, the extical conditions for ignition are achieved primarily by the (external heat ux)” AW provides formulas that relate the sample surface temperature at ignition tthe critical mass flux et ignition for various external heat faxes. The theoretical model developed in AW incorporates all four ignition criteria ‘described atthe beginning of Section 2.13 22.2, Flammability and inition literature review ‘Toe focus of mos of the works dscassed bere i onthe fammatility and ignition of solids and Tigids. AS discussed, mamerous ignition criteria have been used by various researes, one or another according preference Asalso discussed, an actual ignition criterion isch Rader to develop andi requires carefut consideration and analysis 1s far Simple to sever wo a Sandard definition, which singles out one ofthe main physical processes. Thus, Hada and Clark (26.27], Sede [28], Clark [29], Thompson and Deysiale 60] and Thompson ea. (31) employ the eccal cemperaure as the sole ignition rtesc, while Richard ta. 132] and Drysdale and Thompson 33] enploy the ecical ‘as fx and Yang et al (34) employ the limited oxygen index (LOT ASTM D-2863) test None of ese works consider the ritical heat hx for igiton The critical temperature of ignition Ty is the most common quantiative measure of material amsoabity, as ‘escrbed in Chapter 4 af the book by Quintire [17]. la Ret 26}, a discussion is provided of pre-1972 methods for btaining the sutoignition temperature (ce no pl fame) via four methods. These incade the Anbeaius and Semenov 9 Wier Sustained fgkon occurs at = 750, ‘equations, sonnaization of Ty accoxdng 10 ignition delay time and foe guid by injecting a ligui sample into a treated flash in the preseace of air and Chen measuring the lowest temerare at which ignition occurs. This is defined asthe ‘ash? temperature. Tests show a decrease of Ti 20 ‘ig as the flash volume increases, presumably due to 2 reduced surface-o-volume ratio, The reduced surfe-o- ‘volume rao decreases heat losses fom the ask Hilado anc Clark (26) found the largest ascrepancies ia data between combustion engine studies and fe safery seidies, They sugested the adopsion and use of normalized Te, values. The normalization was 19 bo achieved by ‘rouping mo categories of sialer ignition times, sach a 1 1O0t 100, 0 tht “unintntonal bis due to differences apparatus volume and ignition delay time’ may be climinated. Hilado and Clark (27] subsequently compiled 1, valves for over 300 guid organic cheicals. The list provides the lowest reported Ty valu using the glass fiask apparatus discussed in Ref. (25), which amounts to ASTM D 2155 where & metered sample is injected into 2 heeted 200°C glass fask containing air. Fire-proteeuon roups also commonly report lowest values, for obvious reasons. An approximate analytical relation between Ty and ty it provided, slong withthe Arshenias equation decenbing the influcace of temperate on reaction rate, The oqstion takes the form log) = (WT) +B, where A and B are constaas, 1 38 the igntion-delay time and T is the ‘emporatue. This equation is obtained directly from the Semenov equation, Eq. (23). The article also discusses numerous test methods that were developed by organiz~ ations such ¢s ASTM, the National Bureaz of Standards, The US Naval Research Laboratory and various corp ations and universities. Ta contrast to Refs. [26,27], the work of Settle (28) employed » small, orizontel, electrically heated 11S, Wehman / Progress in Erergs ed Conbuston Sence 29 2008) 247-209 29) stainless-steel plate 10 examine Ti, forthe instantaneous (on iota) ignition of rylon, viscose, axle, polypropy- lene @P) and wool, The pate temperature was fixed. the sample and plate touched for2s, thea He pate was lowered ants temperate rose by25°C ut ignition occured upon subsequent two-socond contact, The maximum temperate fornon inition lay between 650°C (for nylon, visas) and "150°C (for wood. The minimam Ti, ranged freon 675°C {@ylen, viscose) to 760°C

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