The Fire Toxicity of Polyurethane Foams: Review Open Access

McKenna and Hull Fire Science Reviews (2016) 5:3
DOI 10.1186/s40038-016-0012-3
REVIEW Open Access
The fire toxicity of polyurethane foams

Sean Thomas McKenna and Terence Richard Hull*
Abstract
Polyurethane is widely used, with its two major applications, soft furnishings and insulation, having low thermal
inertia, and hence enhanced flammability. In addition to their flammability, polyurethanes form carbon monoxide,
hydrogen cyanide and other toxic products on decomposition and combustion.
The chemistry of polyurethane foams and their thermal decomposition are discussed in order to assess the
relationship between the chemical and physical composition of the foam and the toxic products generated during
their decomposition. The toxic product generation during flaming combustion of polyurethane foams is reviewed,
in order to relate the yields of toxic products and the overall fire toxicity to the fire conditions. The methods of
assessment of fire toxicity are outlined in order to understand how the fire toxicity of polyurethane foams may be
quantified. In particular, the ventilation condition has a critical effect on the yield of the two major asphyxiants,
carbon monoxide and hydrogen cyanide.
Keywords: Fire, Combustion, Toxic, Toxicity, Polyurethane, Foam, Decomposition, Asphyxiant, Cyanide, HCN
Introduction are joined by a range of functional groups primarily

Polyurethanes are a diverse family of synthetic polymers derived from the polyaddition of polyisocyanates and
that were first synthesised in 1937 by Otto Bayer. Their polyalcohols. Further reactions occur with amines, water,
development continued commercially in Germany, even- ureas, urethanes and even other isocyanates to produce
tually leading to a global multibillion dollar industry a diverse range of functional groups including urethanes,
(Vilar 2002). The polyurethane market was estimated to ureas, isocyanurates, carbodiimides and uretdiones. A
be worth $33 billion in 2010 and is expected to continue summary of these structures is shown in Fig. 2 (Avar et
to grow to over $55 billion by 2016. Global usage is ex- al. 2012). This range of functional groups and their
pected to expand from 13.65 Mt in 2010 to 17.95 Mt by ratios in the polymer are a large contributing factor to
2016. 95 % of the demand for polyurethanes is situated the wide range of properties that polyurethane materials
in North America, Asian-pacific, and European markets; can possess.
with demand expected to increase in Eastern Europe
and South America in the next 10–15 years. The two
main market uses for polyurethane are in the furniture Cross-linking functional groups
and interior industry and the construction industry with Synthetic polymeric materials may be divided into
28 % and 25 % of the market, respectively (Markets & thermoplastics and thermosets. Thermoplastics are
Markets report 2011). composed of linear polymer molecules, whose shape
can be changed repeatedly on heating and which may
be melted and solidified without chemical change.
Polyurethane chemistry Thermosets are cross-linked polymer molecules
Functional groups which, on heating, do not melt but will eventually
Polyurethanes are named from the presence of the decompose. Most polyurethanes are cross-linked to
urethane (also known as carbamate) functional group some degree and decompose without melting. In
(Fig. 1). Despite their name, the term polyurethane is addition to the more common process of adding
used to describe a family of polymers whose monomers cross-linking reagents during the production process,
cross-linkages in polyurethanes can be the result of
* Correspondence: [email protected]
Centre for Fire and Hazard Science, University of Central Lancashire, Preston the high reactivity of the isocyanate precursors. These
PR1 2HE, UK isocyanate derived cross-links can include biurets and
© 2016 McKenna and Hull. Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0
International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and
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McKenna and Hull Fire Science Reviews (2016) 5:3 Page 2 of 27
Fig. 1 The urethane functional group
allophanates (Fig. 3) (Aneja 2002). Biurets are the re- Fig. 3 Isocyanate derived functional groups that cross-link polyurethane
sult of the reaction of isocyanates with substituted- chains i) biurets ii) allophanates
urea functional groups and allophanates are formed
in small amounts (unless catalysed) by the reaction of
isocyanates with urethanes. Additionally, the self- During polymerisation, isocyanates undergo a num-
addition of isocyanates to produce isocyanurates (v in ber of distinct reactions. Primarily, isocyanates react
Fig. 2), also results in cross-linking in the polymer. Appro- with alcohols to produce urethane linkages in the
priate formulation affords a degree of control over the polymer (Scheme 1). The reaction of an isocyanate
cross-linking in the polymer without the need for functional group with water (Scheme 2) results in the
additional cross-linking agents. formation of an unstable carbamic acid group, which
in turn decomposes to release an amine and carbon
dioxide. This amine may then undergo further reac-
Polymerisation reaction tion with other isocyanates present to produce a urea
Isocyanates are a highly reactive family of compounds (Scheme 3). The carbon dioxide release by the reac-
that are characterised by the R − N = C = O functional tion in Scheme 2 can act as a blowing agent in
group (where R can be any aliphatic or aromatic polyurethane foam production and up to a point the
functionality). The strain of two electronegative atoms amount of water added will be inversely proportional
(N and O) results in electron density being pulled away to the density of the foam. The resulting substituted
from the carbon atom, giving it a strong partial positive urea can then react with another isocyanate to pro-
charge. This makes the isocyanate functional group duce a biuret linkage (Scheme 4). The reaction of a
highly reactive towards nucleophiles with an available urethane with another isocyanate will produce an
hydrogen. These nucleophiles include amines, alcohols, allophanate (Scheme 5).
carboxylic acids, thiols, water, ureas and urethanes Isocyanates also react with themselves in various ways
(Aneja 2002). to produce dimers, trimers and completely new
functional groups. The dimerisation of two isocyanates
is a reversible reaction that produces uretidione ring
(Scheme 6). The trimerisation results in a highly stable
isocyanurate ring which confer additional thermal sta-
bility to polyisocyanurates (Scheme 7). Carbodiimides
are produced by the reaction of isocyanates in the
presence of a catalyst (such as phospholine oxides)
(Scheme 8) (Avar et al. 2012).
These reactions make up the basis of polyurethane
chemistry and can be used to tailor polyurethanes with a
range of properties by varying the structure and ratios of
the individual components.
Fig. 2 Common polyurethane functional groups i) urethane ii) urea Scheme 1 Reaction between an isocyanate and an alcohol to
iii) carbodiimide iv) uretdione v) isocyanurate produce a urethane
Scheme 2 Reaction of an isocyanate with water to produce a carbamic acid which decomposes to produce an amine and carbon dioxide
Isocyanate reactivity isocyanates. Additionally, aromatic isocyanates with

The reactivity of isocyanates with the various functional more steric hindrance are likely to be less reactive
groups commonly present in the production of poly- (such as the 2 position in 2,4-TDI (Fig. 4)). This
urethanes is dependent on both the steric and elec- steric hindrance can be offset by increasing the
tronic factors of the R-group, and also the specific temperature of the reaction or by performing the re-
functional group the isocyanate is reacting with. action in the presence of a catalyst (Vilar 2002).
Table 1 shows the relative reactivity of isocyanates
with nucleophiles at 25 °C without the presence of a Isocyanate precursors
catalyst. This shows that the reactions of isocyanates The isocyanate precursors used in the production of poly-
are much faster with amines and slower with carbox- urethane foams usually consist of aromatic diisocyanates
ylic acids, urethanes and amides than for the alcohols such as toluene diisocyanate (TDI) and methylene diphenyl
used in polyurethane production. An understanding diisocyanate (MDI). Over 90 % of all industrial polyure-
of the relative reaction rates is vital in controlling the thanes are based on either TDI or MDI (Avar et al. 2012).
production of the polymer and producing the desired TDI is produced as the 2,4- and the 2,6- isomer which
physical properties (Herrington & Hock 1998). In this have a boiling point of 121 °C and 120 °C respectively. It is
case, the main reason for including isocyanate reactiv- usually used in isomeric mixtures of varying ratios, with
ity data is to explain the reactivity of isocyanates that 80:20 2,4 to 2,6 being the most commonly used (Fig. 4).
are released into fire effluent during combustion. TDI is primarily used in the production of flexible foams,
Their apparently transient nature results from their which are used in the furniture and interior industries.
very high reactivity with amines and their fairly high MDI is a diaromatic diisocyanate compound that boils at
reactivity with water (which is almost always present 208 °C and is primarily used in the production of rigid
in fire effluent). The presence of both amines and foams. Most rigid foams and speciality polyurethanes use
water in the decomposition products of polyurethane polymeric MDI derivatives which are mixtures components
foams are discussed in later sections. such as dimers and trimers (Fig. 5). Rigid MDI based foams
Isocyanate structure also affects the reactivity of the are primarily used for insulation in the construction indus-
isocyanate group. Bulky substituents that impinge on try and can also be found in the transport industry.
the isocyanate group can reduce its reactivity. Aromatic Other common diisocynates include hexamethylene
isocyanates are more reactive than aliphatic isocyanates diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI)
due to the electronic effects of the aromatic ring. and isophorone diisocyanate (IPDI) (Fig. 6).
Substituted aromatics containing electron withdrawing
groups further increase the reactivity of isocyanates by Polyol precursors
increasing the partial positive charge on the isocyanate As the main reactive group that isocyanates react with,
carbon via a resonance withdrawing effect. polyols are a major component of the resulting polyur-
Aromatic diisocyanates, which are commonly used ethane product. The two main families of polyols used
in the production of polyurethanes, have a slightly are polyether polyols and polyester polyols (Fig. 7) (Avar
more complicated chemistry compared to monoiscya- et al. 2012). Polyether polyols are more resistant to
nates due to the electronic effects of two isocyanate hydrolysis, but less stable to oxidation, while for polyes-
groups. Aromatic diisocyanates ortho- or para- to one ter polyols it is the opposite. As polyols are prepolymers,
another will have an activating effect on each other, their molecular mass is relevant to their application,
thus increasing their reactivity. However, once one of with flexible foams being derived from 1000 to 6000 dal-
the groups forms a urethane or urea, the activating tons and few hydroxyl groups, while those used in rigid
effect on the other isocyanate is reduced, as ureas foams have short chains from 250 to 1000 daltons with
and urethanes are weaker activating groups than high functionality (3–12 hydroxyl groups per chain).
Scheme 3 Reaction of an isocyanate with an amine to produce a urea

Scheme 4 Reaction of an isocyanate with a urea to produce a biuret linkage
Short chains with high functionality results in highly Regeneration of Precursors

cross-linked polyurethane polymers which is characteris- Thermal decomposition of polyurethanes is usually the
tic of rigid foams. reverse of polymerisation, resulting in the formation
their precursor functional compounds—diisocyanates,
Thermal decomposition diamines and dihydroxy compounds. Therefore, the
Inert-atmosphere products of decomposition can be predicted from the
It is generally accepted that the thermal decomposition composition of the polymer. These processes occur at
occurring during flaming combustion is best represented around 300 °C with the precursor chemicals including
by the thermal decomposition of a material in an inert at- TDI, MDI, HDI, polyols (both polyether and polyester-
mosphere. This is due to the concentration of oxygen dir- polyols) and aromatic amines.
ectly under a flame being close or equal to 0 % (Schartel Early work by Woolley et al (1975) indicated that the
& Hull 2007). A large number of studies have been per- decomposition of polyurethanes up to around 600 °C
formed over the last 50 years to understand the thermal resulted in the volatilisation of fragmented polyurethane
decomposition of polyurethane materials, and as a result and subsequent release into a nitrogen rich ‘yellow
of this the mechanism of their decomposition in inert- smoke’, containing partially polymerised isocyanates and
atmospheres is fairly well understood. droplets of isocyanate from the foam. Higher tempera-
tures resulted in the volatilisation of most of the polyur-
Bond stability ethane precursors via the formation of lower molecular
The heating of polyurethanes in an inert-atmosphere weight compounds.
results in the progressive rupturing of bonds as a function Chambers et al. (1981) reported similar data by analysing
of temperature. Biuret and allophanate bonds will decom- the inert-atmosphere pyrolysis of a series of biscarbamates
pose first between 100 and 125 °C. Ureas and urethanes to act as model compounds representing polyurethane
decompose between 160 and 200 °C. Substituted ureas foams. At 300 °C, free isocyanates and alcohols were pro-
decompose between 235 and 250 °C and carbodiimides duced from the decomposition of these biscarbamates. At
decompose between 250 and 280 °C. Isocyanurate rings this temperature around one third of the compounds mass
are the most thermally stable in an inert atmosphere and was lost as volatile products, and the regenerated alcohol
decompose between 270 and 300 °C. A summary of the products were mainly present in the residue of the sample.
bond decomposition temperatures in polyurethanes is Again, above 600 °C the compound and any “yellow smoke”
shown in Table 2 (Gharehbagh & Ahmadi 2012). Al- present was decomposed into smaller volatile fragments.
though these temperatures can provide a good general The study also suggested that any remaining isocyanates
idea of which bonds will be likely to break down with residue would react with themselves to produce polycarbo-
heating, the steric and electronic effects of the attached diimides, thus anchoring the isocyanate precursors in the
groups can affect the strength of the bonds and thus the condensed phase until around 600 °C, where they would
temperature at which the bond will decompose. fragment. While this may occur to some degree, it is
Scheme 5 Reaction of a urethane with an isocyanate to produce an allophanate linkage

Scheme 6 Self-addition reaction of two isocyanates to produce a uretidione
generally accepted that the majority of the diisocyanates also in the condensed phase as a waxy, insoluble white
produced in the decomposition of polyurethanes are ei- substance. This suggests that any amines formed would
ther volatilised or converted into their amine derivative have reacted with isocyanates in the vapour phase to
and then volatilised. form ureas, some of which would have condensed to
Work by Ravey and Pearce (1997) on the decompos- produce the observed waxy white substance. Sub-
ition of a polyether based flexible polyurethane foam ambient differential distillation of the remaining residue
suggested that up to 360 °C the decomposition of the yielded a range of short-chain aldehydes (such as for-
foam was achieved by two main mechanisms. The first maldehyde and acetaldehyde), ketones, alkenes and high
being a depolymerisation which would dissociate the molar mass polyol fragments. The highest concentration
polymer to isocyanates and alcohols, the second being these compounds were formed at occurred at a decom-
dissociation to a primary amine, an olefin and carbon position temperature of 350–400 °C which indicated no
dioxide. The results indicated that the formation of the new degradation steps had occurred beyond 350 °C.
precursor, TDI, was much faster and preferable to Additionally, the authors suggested the positions on the
depolymerisation when the volatile compounds could polyol chain where bond scission could occur, explain-
escape. However, when the TDI was unable to enter the ing the presence of the short-chain alkenes, aldehydes
pyrolysis zone, the slower, irreversible decomposition to and ketones (Scheme 9).
diaminotoluene (DAT) would occur. The authors pro- More recent studies have supported and expanded
posed that once formed, these compounds could par- upon the aforementioned thermal decomposition mech-
tially polymerise with volatilised TDI in the vapour anisms of polyurethane foams. Garrido and Font (2015)
phase to produce Woolley’s “yellow smoke”. Preliminary reported two main steps in the inert-atmosphere decom-
calculations suggested that 27 % of the TDI should be position of flexible polyurethane foams. The first step is
recovered as DAT. Experimental data reported a 28 % the decomposition of the urethane bonds to release and
recovery of DAT which supports the proposed decom- volatilise isocyanates up to 300 °C, with long chain
position mechanism. alcohols being left behind in the condensed phase,
Recent work by Allan et al. (2013) further supported followed by the alcohols degrading at around 400 °C.
the presence of two separate decomposition mechanisms Isocyanates were primarily produced during the first
for flexible foams. The authors noted a primary depoly- stage, and in the second stage primarily carbonyls (R2-C
merisation of the foam which would release volatile TDI = O) and hydrocarbons were detected using infrared
and leave the polyol precursors in the condensed phase. analysis.
Alongside this, the decomposition of the foam into an The difference in the decomposition of rigid and flex-
amine, alkene and carbon dioxide was also proposed. ible polyurethane foams was investigated by Chun et al.
However, no amines were detected in the vapour phase. (2007). They attributed the different decomposition
Instead polyureas were detected in the vapour phase and mechanisms to the physical form of the polyurethane
Scheme 7 Self-addition reaction of three isocyanates to produce a isocyanurate ring

Scheme 8 Reaction of two isocyanates to produce a carbodiimide
foam, rather than to any chemical differences. Rigid content and noted that the yields of HCN were directly
foam decomposed between 200 and 410 °C, while flex- related to the nitrogen content. Work published as early
ible foam decomposed between 150 to 500 °C. The au- as 1959 supported this mechanism of decomposition at
thors reported GC/MS analysis of the condensed phase higher temperatures and noted that up to 70 % of the
products obtained. In both rigid and flexible foams, anil- nitrogen in the foam could be converted to HCN at
ine and p-aminotoluene were reported, which correlates 1000 °C (Saunders 1959).
with the work of Ravey and Pearce (1997) who reported The use of 13C labelling by Chambers et al. (1981) on
that isocyanates that did not volatilise were converted polycarbodiimides and polyureas enabled the determin-
into amines in the condensed phase. Rigid polyurethanes ation of the source of the organonitriles and HCN dur-
primarily produced aromatic compounds in the con- ing thermal decomposition. Their analysis indicated that,
densed phase products of decomposition, whereas flexible above 600 °C, the high temperature decomposition of
polyurethanes produced aromatics, alcohols, aldehydes MDI generated a large number of volatile fragments, in-
and heterocycles. cluding benzene, toluene, benzonitrile and toluonitrile.
Further fragmentation of these molecules led to the pro-
High temperature decomposition duction of HCN, acetonitrile, acrylonitrile and a range of
After the initial stages of inert-atmosphere thermal de- olefinic fragments. The use of 13C labelling in this case
composition where the polymer precursors are reformed allowed the authors to confirm that the nitrogenous
and volatilised, the decomposition products tend to compounds, HCN and organonitriles, originated from
fragment into smaller molecules. Woolley et al. (1972) the thermal fission of the aromatic rings with the nitrile
noted that the yellow smoke was produced up to around carbon being the 2-,4- or 6- carbon of the MDI ring.
600 °C, where it would then decompose to give a family The production of HCN and other low molecular
of low molecular weight, nitrogen containing products weight nitrogenous compounds from the high tem-
including hydrogen cyanide, acetonitrile, acrylonitrile, perature decomposition of polyurethanes has been re-
pyridine, and benzonitrile. The most notable and abun- ported in the literature in recent years. Work by Guo
dant of these was hydrogen cyanide which increased in et al. (2014) on the catalytic decomposition of rigid
yield from 700 to 1000 °C. At 1000 °C the hydrogen polyurethane foam waste showed that ammonia,
cyanide produced accounted for a range of between 3.8 hydrogen cyanide and both nitrogen oxide and nitro-
and 7.3 % by weight. The authors studied decomposition gen dioxide were produced at temperatures up to
at 900 °C of foams, partly decomposed foams, smokes, 1100 °C. Additionally, assorted nitrogenous organics
and pure MDI to assess the hydrogen cyanide (HCN) were detected in the tar including aniline, quinoline,
pyridine, benzonitrile, indole and acridine derivatives
with more than 50 % of the tar nitrogen being bound
Table 1 Relative reactivity of isocyanates with nucleophiles as 4-[(4-aminophenyl)methyl]aniline (the amino analogue
(Herrington & Hock 1998) of MDI). The detection of the amino MDI derivative in
Nucleophile with active Structure Relative reaction rate the tar further supports the literature reports of a
hydrogen (uncatalysed, 25 °C)
Primary aliphatic amine R-NH2 100,000
Secondary aliphatic amine R-NH-R’ 20,000–50,000
Primary aromatic amine Ar-NH2 200–300
Primary hydroxyl R-CH2-OH 100
Water H2O 100
Carboxylic acid R-COOH 40
Secondary hydroxyl R-CH(OH)-R’ 30
Di-urea R-NH-CO-NH-R’ 15
Tertiary hydroxyl (R)3-C-OH 0.5
Urethane R-NH-COOR 0.3
Amide R-CONH2 0.1 Fig. 4 2,4-TDI (i) and 2,6-TDI (ii)
with an increase from 20.8 mg g−1 to 38.0 mg g−1. Simi-

larly, the polyether based foam produced 15.1 mg g−1 to
28.1 mg g−1.
More recent work by Shufen et al. (2006) has sup-
ported the claim that polyether based polyurethanes are
Fig. 5 Methylene diphenyl diisocyanate (MDI)
less stable than their polyester based counterparts when
decomposed in air. The polyurethanes used were
elastomers based on TDI, which could potentially have
secondary decomposition mechanism where isocyanates differing decomposition mechanisms to their foam
trapped in the condensed phase are converted irreversibly counterparts. Thermogravimetric analysis and differen-
into their amine derivatives. tial scanning calorimetry (TGA/DSC) showed that the
A review by Paabo and Levin (1987) found that there polyether based polyurethane began to decompose at
is no difference in the decomposition products of rigid 258 °C, with a second decomposition stage at 350 °C
and flexible polyurethane foams at high temperatures (which could be attributed to the fragmentation of the
regardless of their differing degradation mechanisms at polyether polyol). The polyester based polyurethane
lower temperatures. Both types of foam yielded very began to decompose at 284 °C with a secondary decom-
similar products at temperatures above 600 °C. position step at 359 °C. Overall, the results suggested
that the polyether based polyurethane was less thermally
Oxidative atmosphere stable in the presence of oxygen than the polyester, and
The non-flaming decomposition of non-fire retarded both were generally less stable in air than in a nitrogen
polyurethane foams in air is generally quite well under- atmosphere.
stood and comparable to the inert atmosphere decom- While several authors work has focused primarily on
position, in terms of both products and mechanisms. the nitrogenous products of decomposition, other publi-
Investigations by Woolley et al. (1972) suggested that cations have focused on the production of other com-
the decomposition was initiated by the release of a pounds such as carbon monoxide. Bott et al. (1969)
nitrogen-rich material at 200–300 °C which in turn de- reported the decomposition of rigid polyurethane foams
composes into low molecular weight nitrogenous frag- in both nitrogen and air to assess the production of CO,
ments above 500 °C. Additionally, a polyol-rich residue HCN and NH3. When a one gram sample of foam was
is left behind that begins to fragment and volatilise decomposed in air, CO was formed at a lower
between 300 and 600 °C. The authors noted that the temperature than in nitrogen (300 °C vs 400 °C), with a
polyester polyols were more stable than the polyether relative concentration of 5000 ppm at 500 °C. The for-
polyols, with the latter fragmenting at a lower tem- mation of HCN was at a higher temperature in both air
perature (300–400 °C). Further decomposition occurred and nitrogen (400 °C and 550 °C respectively) with an
about 600 °C with the fragmentation of the “yellow average concentration of 200 ppm at 500 °C. The au-
smoke”, primarily into hydrogen cyanide and small thors suggested that the presence of oxygen does not
quantities of acetonitrile, acrylonitrile and benzonitrile. affect the mechanisms by which CO and HCN are
At higher temperatures the decomposition of the foams produced.
produced increasing amounts of HCN from 600 to 900 °C, In an attempt to improve the understanding of the
followed by a sharp rise between 900–1000 °C. The polyes- thermal decomposition of polyurethanes, Rogaume et al.
ter based foam produced nearly double the amount of (2011) developed a mechanism based on both condensed
HCN between 900 and 1000 °C than the polyether foam and gas-phase decomposition in air. The authors
Fig. 6 Hexamethylene diisocyanate (HDI) (i), 1,5-naphthalene diisocyanate (NDI) (ii) and isophorone diisocyanate (IPDI) (iii)
Fig. 7 A polyether polyol (i) and a polyester polyol (ii)
acknowledged the complexity of the decomposition of HCN, CO, CH4 and CH2O) and PAHs. Polyol fragments
the material but were able to summarise it effectively in in the gas phase will also begin to decompose at >800 °C
a 5-step mechanism (Fig. 8). The presence of oxygen in to produce simple organic fragments and PAHs. In
the atmosphere directly interacts with the solid phase, air, the resulting decomposition fragments can be oxi-
which accelerates decomposition. Each of the decompos- dised into CO, CO2, H2O and nitrogen oxides at high
ition steps took place at a lower temperature in air than in temperatures.
nitrogen, which further suggests the direct interaction of These reactions are accelerated in the presence of
oxygen with the foam during decomposition. By using in- oxygen, which reduces the temperature of the decom-
frared analysis, the authors were able to detect a range of position steps. Polyurethane foams based on polyether
compounds at each step, as summarised in Fig. 8 and polyols will have a lower decomposition temperature in
Table 3. The results of these experiments and the mechan- air than polyester polyol based foams. However, as noted
ism of decomposition derived correlated well with work by Paabo and Levin (1987), many studies into the de-
by Rein et al. (2006) and also Garrido and Font (2015). composition of polyurethane foams do not differentiate
between flaming and non-flaming decomposition, and
focus on the temperature of decomposition rather than the
General decomposition mechanism presence of flames. Therefore, in certain conditions, poly-
Based on the available literature, the non-flaming de- urethanes foams can reach their auto-ignition temperature
composition of both rigid and flexible polyurethane and ignite which will significantly alter the effect the
foams, in both air and nitrogen, can be generalised into decomposition mechanisms and resulting products.
a number of key steps (Fig. 9). The initial decomposition
of the foam, at >300 °C, results in the volatilisation of
isocyanates, amines and Woolleys “yellow smoke”, Assessment of fire toxicity
leaving behind polyols in the condensed phase. These Yields of toxic products from fires
polyols will fragment and volatilise as the temperature Toxic product yields from materials involved in fires de-
increases, leaving behind a char (>600 °C). This char can pend on a number of factors. Material composition,
decompose further, leaving behind a residue at >800 °C, temperature and oxygen concentration are normally the
to produce simple organic fragments and some polycyc- most important. For the purpose of estimating toxicity
lic aromatic hydrocarbons (PAHs). In the gas phase, iso- in fires, fire growth has been classified into a number
cyanates, amines and ‘yellow smoke’ will begin to of stages (ISO 19706 2011):
decompose at >600 °C into low molecular weight nitro-
gen containing fragments (such as benzonitrile, aniline 1. Smouldering combustion
and hydrogen cyanide (HCN)). At >800 °C these com- 2. Early well-ventilated flaming
pounds further fragment into simple molecules (such as 3. Fully-developed under-ventilated flaming
Table 2 Bond decomposition temperatures of the main Although on some occasions smouldering (oxidative
polyurethane functional groups (Gharehbagh & Ahmadi 2012) pyrolysis) can generate toxicologically significant quan-
Bond (see Figs. 2 and 3 for structure) Decomposition temperature tities of effluent (for example smouldering cotton, or
range/°C
polyurethane foam), typically the rate of reaction, and
Allophanate 100–125
hence the amount of toxic species generated will be
Biuret 115–125 small, so it is unlikely to affect anyone outside the im-
Urea 160–200 mediate vicinity. Similarly, well-ventilated fires are gen-
Urethane 180–200 erally small, and of low toxicity. As fires grow, they
Substituted Urea 235–250 become ventilation controlled, and fires in enclosures
Carbodiimide 250–280
such as buildings rapidly change from well-ventilated to
under-ventilated. These fires are large, relative to the
Isocyanurate 270–300
enclosure, and produce greater volumes of effluent,
Scheme 9 Suggested points of chain scission on a polyether polyol resulting in aldehydes, ketones and alkenes (Allan et al. 2013)
affecting occupants over a much wider part of any build- each fire stage can be adequately replicated, and preferably
ing. While well-ventilated fire scenarios are routinely the individual fire stages treated separately.
used for assessment of flammability, because the object
is to stop the fire growing to the out of control stage, Heat, smoke, asphyxiants and irritants
where fire toxicity is concerned, the important fire stages The toxic hazards associated with fire and the inability
are under-ventilated. There are two reasons for this: of victims to escape from fire atmospheres may be con-
sidered in terms of major hazard factors: heat, smoke
1. The volume of effluent is much greater. and toxic combustion products (Hartzell 1993). The
2. The yields of the major toxic products (carbon time available for escape is the interval between the time
monoxide (CO) and hydrogen cyanide (HCN) from of ignition and the time after which conditions become
N containing materials) will be much greater. untenable, such that occupants can no longer take ef-
fective action to accomplish their own escape. This can
Almost all unwanted fires are diffusion flames, with inef- result from exposure to radiant and convected heat; vis-
ficient mixing of fuel and oxygen (as opposed to the ual obscuration due to smoke; inhalation of asphyxiant
"premixed" flames found in burner/combustion systems). gases; and exposure to sensory/upper-respiratory irri-
The interior of large flames are always under-ventilated, be- tants. Fire gases contain a mixture of fully oxidised prod-
cause oxygen cannot penetrate the flame. For any larger fire ucts, such as carbon dioxide (CO2), partially oxidised
there will always be a significant yield of CO, HCN (from products, such as carbon monoxide (CO) and aldehydes,
nitrogen containing materials), hydrocarbons and smoke. fuel and fuel degradation products, such as aliphatic or
Data from large scale fires in enclosures, such as a room, aromatic hydrocarbons, and other stable gas molecules,
shows much higher levels of the two of the major toxi- such as hydrogen halides (HCl, HBr) and hydrogen
cants, carbon monoxide (CO) and hydrogen cyanide cyanide (HCN) (Kaplan et al. 1984a). Heat, smoke and
(HCN) under conditions of developed flaming (Andersson irritant gases may impair escape, increasing the risk of a
et al. 2005; Blomqvist & Lonnermark 2001). It is therefore lethal exposure to asphyxiant gases, and can sometimes
essential to the assessment of toxic hazard from fire that lung damage causes death in those managing to escape.
Fig. 8 5-step decomposition mechanism for flexible polyurethane foam (Rogaume et al. 2011)
Table 3 Products of decomposition of a flexible upon the proportion of the appropriate elements in the
polyurethane foam based on decomposition steps from materials burned and the efficiency of conversion. In
Fig. 8 (Rogaume et al. 2011) general conversion efficiencies are high for halogen acid
Decomposition Gas phase products Condensed phase gases. Most fuel nitrogen is released as N2, but in well-
step products
ventilated combustion conditions a proportion is re-
1 Isocyanates Polyols leased as oxides of nitrogen (mainly NO) and in under-
2 Polyol, CH2O, H2O, Solid residue ventilated combustion conditions a proportion is re-
HCN and CH4 leased as HCN (Purser & Purser 2008a). CO yields are
3 Isocyanates, polyols, Mixed polyol and generally very low for well-ventilated conditions (in the
H2O and CO2 polyol fragments
absence of halogens) but increase considerably under-
4 CO2, CO, H2O, Polyol, Char ventilated combustion conditions. Acrolein and formal-
CH2O, HCN and CH4
dehyde are formed especially from cellulosic materials
5 CO, CO2, H2O, CH2O, CH4, Residue under non-flaming decomposition conditions, but prod-
HCN and small amounts
of polyol. ucts of vitiated combustion contain other organic
irritants.
The main toxic combustion products can be divided Asphyxiant gases

into two classes: asphyxiant gases, which prevent oxygen Asphyxiant or narcotic gases cause a decrease in oxygen
uptake by cells, with loss of consciousness and ultimately supplied to body tissue, resulting in central nervous sys-
death; and irritant gases which cause immediate incapaci- tem depression, with loss of consciousness and ultim-
tation, mainly by effects on the eyes and upper respiratory ately death. The severity of the effects increases with
tract, and longer term damage deeper in the lung. The ef- dose (Hartzell 1993). The main asphyxiants, carbon
fect of asphyxiants and deep lung irritants depend on the monoxide and hydrogen cyanide have been widely stud-
accumulated doses, i.e. the sum of each of the concentra- ied and are the best understood (ISO 13571 2007). In
tions multiplied by the exposure time, for each product; addition, asphyxiation can also occur as a result of low-
upper respiratory tract irritants are believed to depend on ered oxygen concentration, and is affected by the carbon
the concentration alone (Purser 2007). dioxide concentration.
The dangerous concentrations of some important Oxygen depletion can be lethal if the oxygen concen-
toxic fire gases are shown in Table 4 alongside the influ- tration falls below tenable levels (~6 %). However, from
ence of ventilation condition on their yields. The yields a fire toxicity perspective it is generally assumed that
of acid gases and nitrogen-containing products depend heat and other gases will have already prevented
Fig. 9 Generalised decomposition mechanism for polyurethane foams both in nitrogen and in air
Table 4 The main irritant and asphyxiant components in fire gases and their toxic potencies (in terms of incapacitating; and lethal
concentrations) for a 30-min exposure period (ISO 13344 1996: ISO 13571 2012)
Yield largely independent of fire condition Yield decreases as ventilation decreases Yield increases as ventilation decreases
HF (500; 2900 ppm) CO2 (~7 %; ~10 %) also replaces CO (1170 ppm; 5700 ppm)
O2 and
increases respiration rate).
HCl (1000; 3800 ppm) NO2 (170; 250 ppm) HCN (82 ppm;165 ppm)
HBr (1000; 3800 ppm) SO2 (150;1400 ppm) Acrolein (30 ppm;150 ppm)
Formaldehyde (250 ppm; 750 ppm)
Aromatics, aldehydes, ketones etc.
survival, while other toxicants such as CO or HCN, will predominates, or their interrelationship, remains unclear.
be present in lethal quantities further from the fire HCN also causes rapid incapacitation, preventing escape,
where the oxygen depletion would not be considered and then, with CO, contributes to death from asphyxi-
harmful. ation. One analysis of fire victims' blood showed a trend
of declining COHb and a rise in cyanide concentrations
Carbon monoxide (Anderson et al. 1981), probably because of increased use
The toxic effect of carbon monoxide is characterised by of nitrogen-containing synthetic polymers. The uptake,
a lowered oxygen-delivery capacity of the blood, even distribution, metabolism and excretion of cyanide is much
when the partial pressure of oxygen and the rate of more complex than for CO and quantifying CN- in fire
blood flow are normal. Carbon monoxide binds to the victims is more expensive and not routinely undertaken.
haemoglobin in red blood cells resulting in the forma- Therefore the contribution of HCN to fire deaths is diffi-
tion of carboxyhaemoglobin (COHb), with stability 200 cult to assess, and analysis for CN− is limited to cases
times greater than that of oxyhaemoglobin, impeding where lethal concentrations of CO are absent.
the transport of oxygen from the lungs to the cells in
the body. This causes deterioration in mental and mus- Irritant gases
cular performance. CO also combines with myoglobin In contrast to the relatively well-defined effects of asphyx-
in the muscle cells, impairing diffusion of oxygen to iants, the effects of exposure to irritants are more com-
cardiac and skeletal muscles (Purser 2008b). Over short plex. Irritant gases cause pain and breathing difficulties,
periods, inhaled CO impairs an individuals ability to es- leading to incapacitation, such that the victim can no lon-
cape, causing different effects at different concentra- ger effect their own escape (ISO 13571 2012). Sensory and
tions. At a CO concentration of 10 ppm, impairment of upper respiratory tract irritation stimulates the trigeminal
judgement and visual perception occur; exposure to and vagus nerve receptors in the eyes, nose, throat and
100 ppm causes dizziness, headache, and weariness; upper respiratory tract causing discomfort, then severe
loss of consciousness occurs at 250 ppm; and 1000 ppm pain. The effects range from tears and reflex blinking of
results in rapid death. the eyes, pain in the nose, throat and chest, breath-
holding, coughing, excessive secretion of mucus, to
Hydrogen cyanide bronchoconstriction and laryngeal spasms (Purser 2008b).
Hydrogen cyanide is approximately 25 times more toxic At sufficiently high concentrations, or when attached to
than carbon monoxide through the formation of the submicron particles, such as soot, most irritants can pene-
cyanide ion, which is formed by hydrolysis in the blood trate deeper into the lungs, causing pulmonary irritation
(Hartzell 1993). Unlike carbon monoxide which re- effects which may cause post-exposure respiratory distress
mains primarily in the blood (as COHb), the cyanide and death, generally occurring from a few hours to several
ion is distributed throughout the extra-cellular fluid of days after exposure, due to pulmonary oedema (flooding
tissues and organs (ISO 13571 2007). Two mechanisms of the lungs) (ISO 13571 2007)
have been identified for the toxic effects of cyanide.
The first is by combination with the ferric ion in mito- Hydrogen halides
chondrial cytochrome oxidase, preventing electron Hydrogen chloride (HCl) and hydrogen bromide (HBr)
transport in the cytochrome system and inhibiting the are strong acids which dissociate entirely in water. Both
use of oxygen by the cells. The second results in a brief may be present in fire effluent, for example from
stimulation, followed by severe depression, of respira- PVC or halogenated flame retardants, and since the
tory frequency, also starving the body of oxygen, and damage caused by the acidity (the concentration of
causing convulsions, respiratory arrest and death (Alarie H+ ions) is independent of the specific anion (Cl− or
2002). Whether one or other of these mechanisms Br−), the discussion on HCl is also applicable to HBr.
Nitrogen oxides Equation 1 Purser model

Nitric oxide (NO) and nitrogen dioxide (NO2) are non-
½CO ½HCN ½AGI ½OI
flammable gases present in fire effluents. At high con- FED ¼ þ þ þ …
LC50; CO LC50; HCN LC50; AGI LC50; OI
centrations nitric oxide is rapidly oxidised in air to form 21−½O2
nitrogen dioxide, however, at the concentrations found in VCO2 þ A þ
21−5:4
fire gases, most of the nitric oxide remains unoxidised. Ni- expð0:14½CO2 Þ−1
VCO2 ¼1 þ ð1Þ
trogen dioxide dissolves rapidly in water to form nitric and 2
nitrous acid. At high concentrations these acids can cause
pulmonary oedema and death (Paul et al. 2008; Kaplan
1987b). Conversely, nitric oxide gas at low concentra- [AGI] is the concentration of inorganic acid gas irritants
tions (~20 ppm) has been used to aid breathing in the treat- [OI] is the concentration of organic irritants
ment of respiratory disorders (Kavanagh & Pearl 1995). A is an acidosis factor equal to [CO2] × 0.05
This equation only relates to lethality, or cause of

Isocyanates death. However, many people fail to escape from fires
In general, isocyanate (R-NCO) exposure causes irrita- because of the incapacitating effect of smoke (obscuring
tion to the skin, mucous membranes, eyes and respira- visibility) and its irritant components which cause pain,
tory tract (NIOSH 1989). The most commonly reported preventing breathing and escape or reason death oc-
adverse health effects after airborne isocyanate exposure curred. ISO 13571 (2007) considers the four major haz-
is asthma due to sensitisation (Piirilä et al. 2008), where ards from fire which may prevent escape (toxic gases,
inhaled isocyanates rapidly form conjugates with epithe- irritant gases, heat and smoke obscuration). Equations 2
lial lung cell proteins (Wisnewski et al. 1999). Once and 3 have been taken from ISO 13571 (2007). Equa-
sensitisation has occurred, even extremely low concen- tion 2 calculates the FED of the major asphyxiants, CO
trations of airborne isocyanates can trigger fatal asthma and HCN, but without taking oxygen depletion or CO2
attacks (Henneken et al. 2007). driven hyperventilation into account. Equation 3 calcu-
lates the Fractional Effective Concentration (FEC) of
Quantification of toxic hazards from fire sensory irritants in the fire effluent which limit escape.
The general approach in generating toxic potency data Equation 2 represents the generally accepted case that
from chemical analysis is to assume additive behaviour there are only two significant asphyxiant fire gases, CO
of individual toxicants, and to express the concentra- and HCN. The FED value is calculated using the ex-
tion of each as its fraction of the lethal concentration posed dose relationship (concentration-time product,
for 50 % of the population for a 30 min exposure (gas- C∙t) for CO. The incapacitating C∙t product corre-
LC50). Summing these contributions generates a frac- sponds to CO at a dose of 35 000 μL L−1min (ap-
tional effective dose (FED). An FED equal to one indi- proximately equal to ppm min), predicting incapacitation
cates that the sum of concentrations of individual at around 1200 ppm for 30 min exposure, and an expo-
species will be lethal to 50 % of the population over a nential relationship for HCN (because asphyxiation by
30 min exposure. These types of approaches have used HCN exposure does not fit a linear relationship), predict-
existing rat lethality data, as described in ISO 13344 ing incapacitation at around 82 ppm for 30 min expos-
(1996) or more recently, based on the best available ure. However, as fires tend to grow exponentially, they do
estimates of human toxicity thresholds as described in not produce constant concentrations of asphyxiant gases.
ISO 13571 (2007). An equation has been developed for Equation 2 FED model from ISO 13571
the estimation of the FED for lethality from the chem- X
t2
½CO X
t2
expð½HCN=43Þ
FED ¼ Δt þ Δt ð2Þ
ical composition of the environment in the physical t1
35 000 t1
220
fire (such as the bench-scale methods described in the Equation 3 FEC model from ISO 13571
following section) model taken from ISO 13344 (1996)
and uses gas-LC50 values for lethality to provide refer- ½HCl ½HBr ½HF ½SO2
FEC ¼ þ þ þ
ence toxicity data for the individual gases to calculate IC50; HCl IC50; HBr IC50; HF IC50; SO2
toxic potency, based on rats exposed for 30 min. The ½NO2 ½acrolein ½fomaldehyde
þ þ þ
Purser model, presented in equation 1, uses VCO2 a IC50; NO2 IC50; acrolein IC50; fomaldehyde
multiplication factor for CO2 driven by hyperventila- X ½irritant
tion, therefore increasing the FED contribution from all þ ð3Þ
IC50; irritant
the toxic species, and incorporates an acidosis factor A
to account for toxicity of CO2 in its own right (ISO Equation 3 uses a similar principle to equation 1 to
13344 1996). estimate the combined effect of all irritant gases.
In order to relate the fire effluent toxicity to a "max- (Gottuk & Lattimer 2002; Blomqvist & Lonnermark 2001;
imum permissible loading", the FED can be related to Purser & Purser 2008a). The findings from these studies
the mass of material in a unit volume which would cause demonstrated that yields of different toxic products are
50 % lethality for a given fire condition. The fire toxicity highly dependent on equivalence ratio (either positively or
of a material can also be expressed as a material-LC50, negatively correlated), and elemental and molecular com-
which in this case is the specimen mass M of a burning position of the material. To a lesser extent, parameters
polymeric material which would yield an FED equal to such as temperature and oxygen concentration also affect
one within a volume of 1 m3. The relation of the FED to the yields of toxic products.
the material-LC50 is given in equation 4. Most fire deaths and injuries actually occur in residen-
Equation 4 Relation of LC50to FED tial fires, although assessment of fire toxicity is currently
focused on areas where escape is restricted, such as aero-
M
material‐LC50 ¼ ð4Þ planes, railway carriages, and passenger ships, which in-
FED V clude requirements to quantify the fire toxicity of internal
Comparing the toxic potencies of different materials, components. In most countries, there are no regulations
the lower the material-LC50 (the smaller the amount of covering the fire toxicity of building components, or for
materials necessary to reach the toxic potency) the more most road vehicles, including goods vehicles in tunnels. In
toxic the material is. LC50 values should be referenced to China and Japan, there are specific restrictions on the use
the fire condition under which they were measured. of materials with high fire toxicity in high risk applications
such as tall buildings, while an increasing number of juris-
The equivalence ratio ϕ dictions permit the alternative performance based design
The relatively high yields of CO from under-ventilated approaches to fire safety. Reliable rate of heat release, fire
fires are held responsible for most deaths through inhal- effluent toxicity and smoke generation data are all essen-
ation of smoke and toxic gases. However, in the field of tial components of such an assessment. The general ap-
combustion toxicity testing, this under-ventilated burning proach, described in ISO 13571 (2012), is to ensure that
is the most difficult to create using bench-scale apparatus. the available safe escape time (ASET) before escape routes
Research predicting the carbon monoxide evolution become obscured by smoke and/or filled with toxic gases,
from flames of simple hydrocarbons, reviewed by Pitts exceeds the required safe escape time (RSET). Various ap-
(1995), has shown the importance of the equivalence paratus and protocols for quantifying fire effluent toxicity
ratio ϕ. in different jurisdictions and industries have been critically
reviewed (Hull & Paul 2007).
Bench-scale methods for generating toxic effluents

Typical CO
yield (g per g
Bench-scale methods used for generating toxic effluents
of polymer) from polyurethane foams have met with controversy.
actual fuel to air ratio ϕ < 1 fuel lean flames 0.01 Some methods have proved incapable of properly repli-
ϕ ¼ stoichiometric fuel to air ratio cating the most toxic under-ventilated fire condition,
ϕ = 1 stoichiometric flames 0.05
where the yields of carbon monoxide and hydrogen
ϕ > 1 fuel rich flames 0.2
cyanide are greatest, while other methods have shown
good correlation with large scale test data. Bench-scale
methods used for generation of toxic fire effluents ideally
An equivalence ratio of 0.5 represents a well-ventilated should be capable of reproducing individual fire stages
scenario, typical of an early growing fire, while a ratio of or combustion conditions, for input into models of com-
2 corresponds to the under-ventilated stage responsible bustion toxicity. Full-scale fires simultaneously involve
for high yields of toxic effluents. When ϕ = 1 the theor- different fire stages in different places, which are chan-
etical amount of air is available for complete combustion ging with time. However, bench-scale methods which
to carbon dioxide (CO2) and water. allow the combustion conditions to change during the
The relationship between equivalence ratio and yields test are much more difficult to relate to full-scale fires,
of CO and other products has been studied in detail for because the duration of each condition is unknown, and
a wide range of materials during flaming combustion the behaviour of fires changes on scale-up. Most bench-
using two small-scale apparatus designed specifically for scale methods have non-constant combustion condi-
this purpose—the ASTM E2058 fire propagation appar- tions, such as those in closed chambers exposed to a
atus (Tewarson 2002) and the ISO/TS 19700 tube fur- constant source of heat, including the smoke density
nace apparatus (ISO/TS 19700 2013), in conjunction chamber (SDC) (ISO 5659–2 2012), and static tube
with a series of large-scale experiments used for validation furnace tests, such as the NF X 70–100 (2006). Those
with constant combustion conditions are more suited and 50 kW m−2 with piloted ignition. The sample is a
to producing data suitable for comparison and model- 75 × 75 mm square solid sheet and the standard for
ling: the steady state tube furnace (SSTF) (ISO/TS smoke measurement states that the results are only valid
19700 2013) has been specifically designed to achieve at the thickness tested (typically 1–4 mm). For a fixed
this. Intermediate between these two approaches are those chamber volume (0.51 m3), assuming complete combus-
that can produce quasi-steady combustion conditions, tion, the sample thickness will dictate the ventilation
such as the cone calorimeter (ISO 5660–1 2002) with condition, thus a thin sample will burn under well-
non-standardised controlled atmosphere attachment ventilated conditions with minimum toxic products,
(CACC), and the fire propagation apparatus (FPA) (ISO while a thicker sample might be expected to produce a
12136 2011). The difficulty of replicating the conditions of high yield of CO and other products of incomplete com-
fully developed under-ventilated flaming on a bench-scale bustion. The protocol has been modified as a toxicity
is caused by several practical problems. ϕ depends on the test by the mass transport industries, in the aircraft (EN
mass loss rate of the specimen and the available air; for 2826 2011), maritime (Fire Test Procedure Code 2010),
most methods one or both are unknown; ϕ will be in- and railway tests (CEN/TS 45545–2 2009). Some of
creased by an unknown factor if products are recirculated these methods attempt to address the transition through
into the flame zone. Apparatus where ϕ changes rapidly the fire stages by monitoring the formation of toxic
allow little time for sampling and measurement of mass gases as a function of time, as the oxygen concentration
loss and effluent composition at a specific value of ϕ, with falls, and the fire condition changes from well-ventilated
resultant errors and uncertainties. Progressive changes in to under-ventilated. However, unlike a real fire, the heat
the composition of a static specimen (for example due to flux remains constant, and so when the oxygen concentra-
char formation) provide additional complexity. In a com- tion falls, the flame may be extinguished.
partment fire, the reactions of under-ventilated flaming The transport industries have adopted the smoke
occur in both the flame zone and in the hot upper layer. density chamber (SDC) ISO 5659–2 (2012) and ASTM
Only the SSTF has a heated reaction zone which replicates E662, for quantification of toxic product yields (Fire Test
the hot layer. The applied heat flux must be large enough Procedure Code 2010; CEN/TS 45545–2 2009) using
for burning to continue at oxygen concentrations as low simple pass/fail chemical detection (e.g. Draeger tubes),
as 5 %. In some bench-scale apparatus the heat flux is conventional or Fourier transform infrared spectroscopy
constant, and often insufficient to sustain flaming at such (FTIR) gas analysis, despite significant problems of re-
low oxygen concentrations; further, an unknown quantity producibility. It has been suggested that the reproduci-
of fresh air bypasses the fire plume, so the ventilation con- bility problems arise from the single point measurement
dition, and hence ϕ, remains undefined. Some fire models, (the tip of the probe may be in the centre of the plume,
such as the cone calorimeter, fire propagation apparatus below it, or if mixing is more efficient, the upper layer
and smoke density chamber use the temperature of the may be recirculated through the flame), or the timing of
radiant heater to preselect the radiant heat flux, and then the effluent sampling may cause instabilities (for ex-
check this using a radiant heat flux meter. Others, such as ample an initial proposal to sample after 8 min was re-
the NF X 70–100, and the ISO/TS 19700 SSTF use the placed by a proposal to sample when the smoke density
furnace temperature setting to ensure a consistent radiant reached its maximum). The revised protocol is based on
heat flux. The radiant heat flux in the ISO/TS 19700 continuous sampling of the fire effluent.
apparatus has been measured (Stec et al. 2008) and is
40 kW m−2 in the centre of the furnace at 650 °C and The controlled atmosphere cone calorimeter (CACC)
78 kW m−2 at 825 °C. Each method is described briefly in The cone calorimeter (ISO 5660–1 2002) is probably the
the following section. most widely used apparatus for measurement of flamma-
bility properties such as ignitability and heat release rate
The smoke density chamber (Schartel & Hull 2007). It can be used for testing sam-
The most widely used fire-test apparatus, stipulated in ples 100 × 100 mm and up to 50 mm thick, in both the
smoke regulations in most countries of the developed horizontal and vertical orientation. The open cone calor-
world, is the smoke density chamber as described in ISO imeter replicates the early well-ventilated stage of flam-
5659–2 2012, and shown schematically in Fig. 10. Its ing where a fire would be too small to produce enough
widespread availability has encouraged its adaptation to toxicants to cause harm except in very small enclosures.
toxic gas generation and assessment. The standard However, a non-standard modification of the appar-
specifies four test conditions, but fails to link them to atus has been described, enclosing the fire model in a
particular fire scenarios. The conditions specified are: controlled ventilation chamber, in an attempt to repli-
25 kW m−2 without piloted ignition; 25 kW m−2 with cate oxygen-depleted conditions. In this modification,
piloted ignition; 50 kW m−2 without piloted ignition; the controlled atmosphere cone calorimeter (CACC)
Fig. 10 The smoke density chamber (ISO 5659-2) showing a sampling probe for fire smoke toxicity
(Babrauskas et al. 1992), shown in Fig. 11, a conical reduced oxygen concentrations, the fuel lifts from the
heater used as a fire model is enclosed in a heat re- surface, but ignition does not occur (Christy et al. 1995).
sistant glass chamber (400 mm high with 300 × 300 mm Hietaniemi et al. (1999) used the controlled atmosphere
base) so that the air flow around the specimen may be cone calorimeter, but argues correctly, in the authors' opin-
controlled by diluting the oxygen content with nitrogen. ion, that an instantaneous “effective” global equivalence
In some cases the effluent continues to burn as it emerges ratio ϕeff, should be used, rather than an averaged local
from the chamber, (secondary flaming in Fig. 11) ultim- equivalence ratio, based on the oxygen supply to the cham-
ately giving well-ventilated flaming. In others, under ber, because, in some experiments, substantial secondary
Fig. 11 The controlled atmosphere cone calorimeter

flaming occurred outside the test chamber, such that the compared to published large-scale enclosure fire data
amount of oxygen available to combustion exceeded the (from a standard ISO 9705 room) for two polymers,
amount that was fed to the enclosed chamber. polypropylene (PP) and polyamide 6.6 (PA 6.6). The re-
sults from the SSTF and FPA show the best agreement
The steady state tube furnace (SSTF) with those from the full and 1/3 scale ISO room for both
The steady state tube furnace (ISO/TS 19700 2013), materials under a range of fire conditions. The CACC
shown in Fig. 12, feeds the sample (typically around 25 g and SDC show reasonable agreement for well-ventilated
of pellets or granules) into its hot zone at a fixed rate, burning, but fail to replicate the more hazardous
under a controlled air supply, inside a horizontal silica under-ventilated fire conditions. The NFX generates data
tube of diameter 48 mm, allowing adequate mixing of intermediate between the well-ventilated and under-
fuel and oxidant. It forces combustion by driving the ventilated fire conditions.
sample into a furnace of increasing heat flux at a fixed
rate, so that, by running several tests with the same Toxic products formed during flaming combustion of
material with different ventilation conditions, each fire polyurethane foams
stage can be replicated by steady state burning. The In the UK, the rapid rise in fire deaths, in particular
products generated in the flame zone then pass through those from smoke toxicity, between the late 1950s and
the heated furnace tube, maintaining a high temperature, the early 1980s has been attributed to the rapid growth
as in the upper layer of a compartment fire. The toxic in low cost polyurethane foam furniture, with superior
product yields may be quantified from the gas concen- comfort and lower cost than the natural fillings that pre-
trations and mass feed rate during the steady state burn ceded it. The higher flammability of these new furniture
period. It has been designed to generate data for input products took people by surprise, and has been blamed
to fire hazard assessments, using the methodology in for an increased number of serious fires and a tripling of
ISO 13344 (1996) and ISO 13571 (2012), particularly in fire deaths over 20 years (Fig. 13) (UK Fire Statistics
relation to the ISO fire stages. The sample is spread 2013).
evenly in a silica boat over a length of 800 mm and fed Over this period there was a corresponding shift from
into a tube furnace at a typical rate of 1 g min-1 with the main cause of death in fires being attributed to
flowing air at a rate of 2-10 L min-1. Secondary air is “burns” to being attributed to “inhalation of smoke and
added in a mixing chamber to give a total gas flow of toxic gases”. Further to this, a similar pattern began to
50 L min−1. emerge in the injuries of fire victims (Fig. 14) (UK Fire
Statistics 2013).
Relationship to full-scale fires The yields of some of the most toxic gases from un-
The yields of CO and HCN from five bench-scale wanted fires (such as CO, HCN and some organic irri-
methods have been compared to large-scale data under tants) have been demonstrated to be directly related to
a range of flaming fire conditions (Stec & Hull 2014). the combustion conditions (Purser 2002). In the case of
Toxic product yield data from the smoke density cham- flaming combustion, one of the most important factors
ber (ISO 5659–2 2012), the controlled atmosphere cone relating to the toxic product yield is the fuel/air ratio
calorimeter (based on ISO 5660–1 2002), the fire propa- which, as defined earlier, can be expressed as an
gation apparatus (FPA) (ASTM E 2058), the French equivalence ratio (ϕ). As the availability of oxygen
railway test (NFX) (NF X 70–100 2006), and the steady becomes lower in proportion to the amount of fuel,
state tube furnace (SSTF) (ISO/TS 19700 2013) were the yields of certain toxic gases will increase. In
Fig. 12 The Steady state tube furnace apparatus, ISO/TS 19700

Fig. 13 Causes of UK fire deaths from 1955 to 2013 (UK Fire Statistics 2013)
ventilation controlled fires (such as those occurring in Stec and Hull (2011) assessed the fire toxicity of build-
a room, building or other enclosure), the yields of ing insulation materials using a steady state tube furnace
these gases from the flaming combustion of polyur- as described in ISO/TS 19700 (2013). The samples
ethane foams generally follow the same trend. As a tested included both commercial rigid polyurethane
result of this, studies that use ventilation controlled foam and polyisocyanurate foam. Under well-ventilated
conditions, such as those using the steady state tube flaming (ϕ < 0.8), the yields of CO2 and NO2 were at
furnace (ISO/TS 19700 2013), are more likely to give their highest, while the yields of CO and HCN were at
a realistic representation of these reduced oxygen en- their lowest. However, as the fire condition became
vironment fire conditions. under-ventilated (ϕ > 1.5), the yields of both CO and HCN
Fig. 14 Non-fatal UK fire injuries requiring hospital treatment, 1955-2013 (UK Fire Statistics 2013)
Table 5 Toxic product yields the flaming combustion of a rigid in these experiments) would occur more readily during
polyurethane foam and polyisocyanurate foam (Stec & Hull 2011) well-ventilated burning. The authors noted no significant
Material Furnace ϕ CO HCN difference in the range of yields of isocyanates detected
temperature (°C) Yield/mg g−1 Yield/mg g−1 in either well- or under-ventilated conditions with a
Rigid Polyurethane 650 0.69 60 6 range of 1.0-1.6 mg g−1.
Foam
650 1.24 220 9 Very few authors have assessed the yields of isocya-
825 2.00 240 12 nates produced during the flaming combustion of poly-
Polyisocyanurate 650 0.75 80 7
urethane foams and as such there is a limited amount of
Foam data available. Investigations by Hertzberg et al. (2003)
650 1.34 220 10
used a cone calorimeter to assess the yields of amines,
825 1.97 225 17 aminoisocyanates and isocyanates from the flaming
combustion of a flexible polyurethane foam. The aver-
increased for both rigid polyurethane and the polyisocya- age combined yield of isocyanates recovered was
nurate, while the yields of CO2 and NO2 decreased. The 0.869 mg g−1 and the average yield of amines and
yields of CO and HCN at varying ϕ and temperature are aminoisocyanates was 0.321 mg g−1. These yields are
presented in Table 5. For both materials there is a clear in- comparable to that of the results reported by Blomqvist
crease in yield from the well-ventilated to under- et al. (2007). Additionally, the authors reported a yield of
ventilated conditions. The rigid polyurethane foam pro- 13–15 mg g−1 of CO, 1.4–1.5 mg g−1 of HCN, and 10–
duced slightly more CO than the polyisocyanurate at ϕ 12 mg g−1 of NO. The authors noted that the yields of the
~2.0 (240 mg g−1 vs 225 mg g−1). The polyisocyanurate, toxicants produced an atmosphere in the tests which fell
on the other hand, produced slightly more HCN than the well below their Immediately Dangerous to Life and
rigid foam (17 mg g−1 vs 12 mg g−1). Additionally, the Health (IDLH) values. However, the lower yields can be
amount of CO generated for both materials began to taper attributed to the fact that the cone calorimeter is a well-
off at ϕ 1.2-2.0 as the available oxygen becomes so low ventilated scenario, estimated as ϕ ~0.7 (Schartel & Hull
that the generation of CO becomes limited, while the yield 2007). Taking this into consideration, the reported yields
of HCN continues to increase with equivalence ratio of isocyanates, aminoisocyanates and amines are still rele-
and temperature. The authors noted that the yields of vant, as the results of Blomqvist et al. (2007) suggests that
CO during the well-ventilated testing were higher their yields are not heavily dependent on the ventilation
than expected for both materials, and attributed this conditions and that the yields would likely only increase
to the possible presence of gas phase free radical by a small amount during under-ventilated flaming.
quenchers, such as halogens or phosphorous contain- While the link between CO yield and equivalence ratio
ing flame retardants, which would reduce the conver- is well established, the yield of HCN in ventilation lim-
sion of CO to CO2 (Schnipper & Smith-Hansen ited conditions shows more complicated behaviour for
1995). polyurethanes. While it is evident that the HCN yield
In another investigation, using a steady state tube fur- increases as a fire becomes more under-ventilated, the
nace, Blomqvist et al. (2007) assessed the toxic product link between the nitrogen content of the fuel and the
yields of a flexible polyurethane foam that was designed yield of HCN is less clear. In a series of investigations,
for use in hospital mattresses. The test conditions were Purser and Purser (2008a) examined the yields of HCN
designed so that the fire conditions met the ISO 19706 from a range of materials and the conversion of fuel ni-
(2007) fire type 2 (well-ventilated flaming fire ϕ < 0.75) trogen to HCN. A "combustion modified high resilience"
and fire type 3b (post-flashover fire in large or open flexible polyurethane foam (CMHR-PUF) and a polyiso-
compartments ϕ ~2.0). The yields of toxic products cyanurate (PIR) foam were analysed a steady state tube
followed the expected trend of being higher in the furnace apparatus. Tests were carried out on the
under-ventilated conditions. The average well-ventilated CMHR-PUF at 650 °C and 850 °C and at 700 °C for the
yield of HCN was found to be 4 mg g−1, while it was PIR in order to achieve steady flaming conditions. Both
9 mg g−1 for under-ventilated conditions. The peak of the materials showed a clear relationship with the
HCN value reached was 10 mg per g−1 in the under- HCN yield increasing with ϕ. At 650 °C, the yield of
ventilated tests. The yield of CO had a wide range dur- HCN from the CMHR-PUF increased up to ϕ ~2.0
ing the under-ventilated tests due to inconsistent flam- where it reached a peak of 14 mg of HCN per gram of
ing of the sample with yields from 100–250 mg g−1. polymer burned. However, when ϕ >2.0 the yield of
Additionally, NO was detected during the well- HCN decreased, falling to 10 mg g−1 at ϕ ~2.75. At
ventilated tests and NH3 during the under-ventilated 850 °C the yield of HCN was higher with 16 mg g−1 at ϕ
tests. This agrees with the fact that oxidation of NH3 ~2.0. The PIR foam produced similar HCN yields to the
and HCN to NO (and NO2, although it was not analysed CMHR-PUF until ϕ 1.5, after which it increased more
rapidly to give a yield of 20 mg g−1 at ϕ ~1.75. This The results showed a HCN yield of 15.8 mg g−1 at 600 °C.
value decreased to 18 mg g−1 at ϕ ~2.0. The yield was much lower at 800 °C with 7.4 mg g−1
Elemental analysis of the polymers showed that the but at 1000 °C and 1200 °C the yield increased
CMHR-FPUR contained 8.22 % nitrogen by weight and significantly to 33.9 mg g−1 and 48.1 mg g−1 respect-
the PIR contained 6.15 % nitrogen by weight. Based on ively. The specific mass of the polyurethane sample
this data, the HCN recovery fraction was calculated for was not provided by the author and the ventilation
both materials. The PIR at ϕ 1.75 resulted in 15 % of the conditions were not clear as a result of this. The signifi-
fuel nitrogen being recovered as HCN. At ϕ ~2.0 the cant increased yields at 1000 °C and 1200 °C could also
CMHR-FPUR resulted in 8 % and 11 % nitrogen recov- be attributed to pyrolysis of the nitrogenous combustion
ered as HCN for 650 °C and 850 °C respectively. The products into HCN due to the low air flow rate.
authors acknowledged that the lower nitrogen recovery In many studies (such as those by Stec and Hull
fraction for the flexible foam could be due to fuel ni- (2011), Purser and Purser (2008a) and Blomqvist et al.
trogen being lost as isocyanates, which are known to (2007)), the sample is raised to a fixed furnace
escape into the effluent plume, while for rigid foams temperature, which is further increased in the gas phase
they are more likely to be trapped in the burning solid during flaming combustion. This will result in a HCN
(Woolley & Fardell 1977). For the range of materials yield related that specific furnace temperature. However,
investigated, the authors also noted that those contain- during the combustion of polyurethane foams, the HCN
ing fire retardants (including the CMHR-PUF and PIR) yield is notably higher when the fire progresses from
resulted in a higher recovery fraction of fuel N as smouldering to flaming combustion. This was observed
HCN. Similarly to the trend reported by Stec and Hull by Levin et al. (1985) when a flexible polyurethane foam
(2011) in well-ventilated conditions, this can be attributed was first heated at a temperature below its auto-ignition
to gas phase free radical quenching in the material by the temperature, followed by flaming combustion of the
chlorine present in both the CMHR-PUF and PIR (2.53 % remaining char and residue at a higher temperature. The
and 3.56 % chlorine by weight, respectively). authors intended to compare the HCN yields for the
Alongside the experiments performed in the steady non-flaming and flaming combustion of the foam in a
state tube furnace, the PIR was also investigated in a half smoke chamber apparatus (as described in Levin et al.
scale ISO 9705 room-corridor test and in a full size ISO 1982) to that of a large scale test room. The test room
9705 (1993) room. During these tests, the PIR was set was 2.4 × 3.0 × 3.0 m with a door (dimensions not speci-
up as wall panels covered on two faces with aluminium fied) and a 1 to 2 kg slab of foam in the centre of the
foil. The cribs used in the ISO 9705 tests were con- room. Smouldering was forced by an electrically heated
structed from PIR “sticks” which burned rapidly, albeit resistance wire embedded in the sample and a load cell
with minimal damage to the room. The full size ISO measured the mass of the sample throughout the experi-
9705 test resulted in well-ventilated flaming (ϕ 0.26–0.5) ment. In the smoke chamber, the highest reported yield
due to the relatively large volume of air and relatively during flaming combustion was 1.02 mg g−1. In the large
small sample size. The full-scale test showed good ac- scale test room, the sample smouldered for 1.5 to 2 h,
cordance with the SSTF data considering the inherent resulting in a HCN yield of 1.03 mg g−1. Once the material
unreliability of large-scale testing. The half-scale ISO ignited, the yield of HCN increased to 3.8 mg g−1. While
9705 experiments showed a wider range of ventilation the smoke chamber experiment is known to give low
conditions up to ϕ ~2.0. However there was significant HCN yields, and both scenarios are well-ventilated, the
scattering of the results with both high and low outliers yield of HCN was almost 4 times as high during flaming
(26 mg g−1 at ϕ 1.22 and 9 mg g−1 at ϕ 1.95). Taking combustion if the sample was allowed to smoulder first.
into consideration the issues with repeatability of large- This prompted the authors to perform further studies
scale testing, the authors asserted that the similar trend in order to understand why allowing the foam to
in HCN yields supported the good relationship between smoulder increased the yield of HCN during flaming
the tube-furnace and large-scale results. combustion. Using a cup furnace with a 200 L sampling
The increased yield of HCN for the CMHR-FPUR be- chamber (identical in design to the one used in the
tween 650 °C and 850 °C is likely due to the increased frag- smoke chamber experiments), a 3.88 g sample of
mentation of nitrogenous organic compounds in the flame, foam was heated to just below its ignition
similar to the behaviour during non-flaming combustion in temperature (370 °C) which yielded <1 mg g−1 HCN.
air reported by Woolley et al. (1972). Michal (1982) In the chamber, 0.23 g of black char and 0.04 g of
reported a similar trend at a fixed air flow rate. A sample of yellow oil were recovered. When the black char was
rigid polyurethane foam was heated in a static tube furnace burned at 600 °C, it yielded 14.95 mg of HCN
with an air flow of 50 ml min−1 at a range of temperatures (65 mg per gram of char) and the yellow oil yielded
from 600 to 1200 °C and the yield of HCN was quantified. 21 mg per gram of oil. Elemental analysis of the polymer
and the char showed that 80 % of the nitrogen in the poly- resulted in deaths post-exposure. The authors noted that
mer was lost when heated at 370 °C, but only 0.6 % was rein both the flaming and non-flaming combustion of the
covered as HCN when burned at 600 °C. However, while polyurethane foam, the concentrations of toxicants did
the char produced when the polymer was heated at 370 °C not reach high enough concentrations to predict deaths.
contained only 20 % of the total nitrogen from the polymer, The polyester fabric produced 92–93 mg g−1 of CO
40 % of that (8 % of the total nitrogen in the polymer) was when burned with very little difference in the flaming or
recovered as HCN when the char was burned at 600 °C. non-flaming conditions. This was enough to cause
This suggests that the nitrogen in the char will more readily deaths both during and post-exposure. When tested with
form HCN, even when the flaming is well-ventilated. the polyester covering the polyurethane, the yield of
The amount of nitrogen recovered from the char (8 %) at HCN during flaming combustion was higher than that
600 °C is of a similar order to the results reported by Purser of just the polyurethane foam on its own. However, the
and Purser (2008a) in the steady state tube furnace suggest- yield of CO was lower in both the non-flaming and
ing that the amount of nitrogen in the polyurethane foam flaming combustion. The overall toxicity of the com-
converted into HCN when the material is allowed to bined materials was higher, and the average concentra-
smoulder first before flaming is similar to that of steady tions of the gases throughout the tests were consistently
under-ventilated flaming. In a report from the same labora- higher than that of the individual materials in both flam-
tory, Braun et al. (1990) also reported increased HCN yields ing and non-flaming conditions. The authors noted that
when the sample was allowed to smoulder before flaming the total concentrations of CO and HCN during flaming
in similar apparatus as above. In a real fire, involving cycles combustion were greater than the sum of those from the
of growth and decay of flaming combustion, the resulting individual materials. It is difficult to draw more general
yields of HCN from the combustion of polyurethane foams conclusion from this work because the fuel-to-air ratio
are likely to be higher than predicted in some bench-scale was not quantified, and the degree of mixing of fresh air
methods as a result of this two-step decomposition and fire effluent, in the exposure chamber, is unknown.
mechanism. However, it does suggest that yield of toxic products is
The widespread use of flexible polyurethane foams in effected by covering the foam with another material dur-
furniture and other upholstery, where they are usually ing flaming combustion.
covered in some kind of fabric has prompted some Similarly, Busker et al. (1999) tested both rigid and
authors to investigate the effects of covering the foam flexible polyurethane foams using a bespoke smoke
on the yield of toxic products. Levin et al. (1986) investi- chamber apparatus to assess the toxicity of the flaming
gated the toxicity of flexible polyurethane foam and a combustion products of the materials to rats. The
polyester fabric both separately and together. Using a samples were heated at 800 °C in a static tube fur-
smoke chamber set up for animal exposure experiments nace, with the effluent being cooled to <50 °C before
(as described in Levin et al. 1982), the authors exposed entering an exposure unit. The rigid polyurethane
male Fisher 344 rats in a 200 L exposure chamber to the foam yielded ~55 mg g−1 CO and ~0.5 mg g−1 of
fire effluent from the flaming and non-flaming combus- HCN. The flexible foam produced ~175 mg g−1 of
tion of both materials. The reported yields were ex- CO and 5 mg g−1 of HCN. The authors also noted
tremely low for both CO and HCN, as the NBS smoke that the presence of aldehydes was detected during
chamber apparatus is a well-ventilated fire scenario re- the flaming combustion of the flexible foam, albeit in
ported to give low HCN yields (Table 6). Flaming com- extremely low yields. Based on the temperature of the
bustion of the polyurethane foam did not cause any test, the yields of HCN are extremely low when
animal deaths, however the non-flaming combustion compared with the CO yields. The authors did not
Table 6 Concentrations of CO and HCN from flexible polyurethane foam, polyester fabric and polyester fabric on polyurethane
foam (Levin et al. 1986)
Flaming/non-flaming Material CO HCN
and temperature
Concentration/ppm Yield/mg g−1 Concentration/ppm Yield/mg g−1
Non-flaming Polyurethane Foam 740 22.8 9 0.3
374–377 °C Polyester Fabric 2910 93 - -
Polyester Fabric on Polyurethane Foam 1390 33.28 5 0.12
Flaming Polyurethane Foam 840 26.0 27 1.515
523–527 °C Polyester Fabric 2990 92.2 - -
Polyester Fabric on Polyurethane Foam 3070 75.72 63 1.87
specify which analytical methods were used in the ventilated conditions. The authors made this assertion
quantification of the fire gases, only that they were based on the yield of average CO from post-flashover
sampled via a sampling bag. fires being 200 ± 9 mg g−1. HCN analysis was performed
Several authors have investigated the relationship be- using infrared (IR) spectroscopy using a short path-
tween bench-scale test data and large-scale test data using length gas cell, which is a questionable method for the
polyurethane foams. Babrauskas et al. (1991a) compared a quantification of HCN due to its poor IR absorption,
number of test methods. The authors tested a rigid poly- high potential for interferences and a poor limit of de-
urethane foam using a NBS cup furnace (as described in tection. This resulted in the reported HCN yields for the
Levin et al. 1982), a developmental method (SwRI/NIST under-ventilated conditions being lower than expected
method) which used a radiant heater on the sample which in all of the tests. Taking this into consideration, the
lead into a 200 L exposure chamber, a cone calorimeter steady state tube furnace and the controlled atmosphere
(ISO 5660 2002), a furniture calorimeter (as described in cone calorimeter both produced the highest yields of
Babrauskas et al. 1982), and a three-compartment large HCN in under-ventilated conditions.
scale test. The three-compartment test consisted of a The authors acknowledged that further investigation
2.4 × 3.7 × 2.4 m burn room, a 2.4 × 4.6 × 2.4 m corridor of the steady state tube furnace was warranted as in
and a 2.4 × 3.7 × 2.4 m target room where samples would some of the testing they suspected an instrumental error,
be taken. The three compartments were connected by since they were unable to account for roughly two-thirds
doors and the target room contained an open vent. Al- of the total carbon from the sample and detected un-
though the authors intended for the bench scale test usually low levels of CO2 during the under-ventilated
methods and the large scale test to represent post- tests. While there were some problems, the data does
flashover room fires, the tests resulted in CO and HCN show that the yields of toxicants from the polyurethane
yields that suggested the combustion conditions were not foam were generally most representative of post-
under-ventilated (Table 7). The test method that produced flashover conditions in the test methods that were de-
toxic product yields associated with under-ventilated flam- signed for ventilation controlled conditions, such as the
ing was the NBS cup furnace toxicity method, which steady state tube furnace and the controlled atmosphere
yielded 180–210 mg g−1 of CO and 16–20 mg g−1. This is cone calorimeter.
unusual as this test method is usually well-ventilated and As polyurethane foams have very low thermal inertia, ap-
the results are not similar to reports of other authors plication of heat or a small flame can be enough to ignite
(such as Levin et al. 1985 and Levin et al. 1986). them. In order to reduce the ignitability, and to a less extent
A more recent assessment by Marsh and Gann (2013) the surface spread of flame and peak heat release rate, fire
tested a flexible polyurethane foam with a cotton polyes- retardants are commonly added to commercial polyureth-
ter cover in a range of test methods including the radi- ane foams in order to meet specific regulatory demands. A
ant heat apparatus (NFPA 269 2012), the ISO 5659–2 comprehensive review of fire retardants and their use in
(2012) smoke density chamber, a controlled atmosphere polyurethane foams was published by Singh and Jain
cone calorimeter (ASTM E 1354) and the steady state (2009). The review refers to a publication by Babrauskas et
tube furnace (ISO/TS 19700 2013). The authors pre- al. (1991b) wherein polyurethane containing a phosphate
sented a large set of data for all of the test methods, in- fire retardant caused immediate death of all of the animals.
cluding a range of test conditions, air flow rates, oxygen Early work by Voorhees (1975) identified what they de-
concentration, and mass loadings. The reported yields scribed as ‘extreme toxicity’ of the combustion products of
for the tests performed can be found in Table 8. The ra- a phosphate fire retarded polyurethane foam. Voorhees
diant heat apparatus, smoke chamber and controlled at- suggested that the compound was a bicyclic phosphate
mosphere cone calorimeter produced much lower CO compound and noted grand mal seizures followed by death
yields than would be expected for under-ventilated flam- in rats with a loading as low as 4 % by weight of the fire
ing. The steady state tube furnace produced a CO yield retardant. Analysis of the compound, trimethylol propane
that was closer to what would be expected for under- phosphate (TMPP), by Kimmerle (1976) found it to have a
Table 7 Comparison of yields of CO and HCN for a series of tests (Babrauskas et al. 1991a)
Test method Test conditions CO Yield/mg g−1 HCN Yield/mg g−1
NBS Cup Furnace Method 550 °C 180–210 16–20
−2
SwRI/NIST Method 50 kW m 80–120 1.9–4.4
Cone Calorimeter Method Range for 35–75 kW m−2 42–80 4–5
Furniture Calorimeter 330 × 330 × 254 mm crib, 1.0 kg 80 N/a
Three-compartment Room Test See description in text 100–140 5–11
Table 8 Yields of CO and HCN from a range of test methods (Marsh & Gann 2013)
Test type Test variables CO Yield/mg g−1 HCN Yield/mg g−1
Radiant Furnace Initial Oxygen %
21 28 <3.0
17 36 1.0
Smoke Density Chamber Irradiance/kW m−2 Pilot
50 Unpiloted 19 3.4
50 Piloted 66 1.0
25 Piloted 43 6
Steady State Tube Furnace Temperature
650 °C (well-ventilated) 26 <3.0
825 °C (under-ventilated) 143 8.8
−2 −1
Controlled Atmosphere Cone Calorimeter Irradiance/kW m Air Flow/L s Initial Oxygen %
50 25 21 27 3.7
18 35 7.7
16 44 12.5
50 12.5 21 24 3.6
16 35 9.6
14 33 3.9
25 25 21 24 -
18 29 -
16 29 -
high acute toxicity when tested on rats. The formation of Since then, Blais and Carpenter (2015) investigated a
the toxicant in question was the result of an unusual reac- flexible polyurethane foam with and without a chloro
tion of the polyol in the foam, trimethylol propane, with phosphate (tris-dichloro-propyl phosphate TDCPP) fire
the phosphate fire retardant in the gas phase. retardant using a smoke box (ISO 5659–2 2012) to assess
Paabo and Levin (1987) reviewed the literature of the the toxicity. The authors asserted that fire retarding flexible
toxic product generated by the combustion of rigid poly- polyurethane foam did not increase its acute or chronic
urethane foams. The review suggested that the addition toxicity when compared to non-fire retarded flexible foam.
of fire retardants did not appear increase the overall They also asserted that the toxicity of the fire retarded foam
combustion toxicity of polyurethane foams. However, was less than or equal to wood on a mass/mass basis and
this did not take into consideration the incapacitating that wood contributes significantly more to residential fires
effects of the release of irritant gases. A more recent in terms of fire smoke toxicity. However, due to the poor
review, by Levchik and Weil (2004), assessed the decom- reproducibility of smoke chamber experiments, the ten-
position, combustion and fire-retardancy of polyure- dency for it to give very low HCN yields, and the fact that
thanes. The author acknowledged that there is a range the experiment is well-ventilated, the reported toxicity is
of contradictory results available in the literature regard- likely much lower than in a real fire situation. In a letter to
ing their fire toxicity. It is likely that the fire toxicity of the editor of the journal, Barbrauskas et al. (2015) ques-
fire retarded polyurethane materials is largely dependent tioned their methodology and noted that the authors did
on the specific fire retardant present. For example, Levin not address the release of HCl and its contribution to the
and coworkers reported that melamine-treated flexible acute fire toxicity of the fire retarded foam.
polyurethane foam generated 6 times more HCN than Historically, material-LC50 data has been reported dir-
an equal amount of non-melamine treated foam. How- ectly based on animal lethality testing, however due to
ever, the presence of Cu2O reduced the HCN generated the declining use of animal testing in fire toxicity assess-
by the flexible polyurethane foam by 70-90 % at low ment, calculations based on standard lethality data (such
temperatures. The authors associated this with the ef- as ISO 13344 1996) are more commonly used. As the
fects of the Cu2O catalytically oxidising the HCN into toxic product yields of polyurethane foams are directly
N2, CO2, H2O and a small amount of nitrogen oxides. related to the ventilation conditions, so is the materials
Table 9 Fire Toxicity of polyurethane foam and polyisocyanurate Table 10 LC50 values for well-ventilated flaming combustion
foam in a range of conditions, represented as a material-LC50 (Neviaser & Gann 2004)
(Stec & Hull 2011) Material Reference Material-LC50
Material Fire conditions ϕ Material-LC50/g m−3 (30 min + 14
day post)/g m−3
Polyurethane Foam Smouldering - 337.2
Flexible Polyurethane Foam
Well-ventilated 0.69 15.7
NFR FPU #12 Levin et al 1983a 40.0
Under-ventilated 1.24 10.3
FR FPU #11 Levin et al 1983a 40.0
No details provided Babrauskas et al 1991b 52.0
Polyisocyanurate Foam Smouldering - 498.4 Melamine type foam Babrauskas et al 1991b 12.5
Well-ventilated 0.75 16.5 Melamine type foam Babrauskas et al 1991b 26.0
Under-ventilated 1.34 10.7 with vinyl fabric
FR FPU #14 Levin et al 1983a 27.8
FR foam- 22.3 kg m−3 Braun et al 1990 26.0
FR GM-23 Farrar et al 1979 34.5
LC50 value. Stec and Hull (2011) presented material- FR GM-27 Farrar et al 1979 33.1
LC50 data for rigid polyurethane foam and polyisocyanu- NFR FPU #13 Levin et al 1986 40.0
rate foam, calculated using rat lethality data from ISO NFR foam 22.3 kg/m−3 Braun et al 1990 40.0
13344 (1996). A summary of these results can be found NFR GM-21 Levin et al 1983b 38.0
in Table 9. The overall toxicity of the polyisocyanurate
NFR GM-21 Levin et al 1983b 49.5
foam shows a clear increase as the fire became more
under-ventilated, while the rigid polyurethane foam
NFR GM-21 Farrar et al 1979 43.2
showed a slight decrease at ϕ 1.24—2.00. This slight de-
crease is probably within the limits of experimental NFR GM-25 Farrar et al 1979 37.5
error, as it does not follow the general trend shown by NFR Foam Farrar & Galster 1980 43.2
most materials. Using the methodology in ISO 13344, NFR Upholstered Chairs Barbrauskas et al. 1988 35.0
with FPUR, cover fabric
the authors also calculated the fractional effective dose and steel frame. Foam
(FED) of the individual toxicants sampled. The FED is density: 25 kg m−3
expressed as the sum of contributions to toxicity from Rigid Polyurethane Foam
individual species and normalised to 1 g of fuel in 200 L NFR Foam, 25 mm thick, Babrauskas et al 1991a 11.0
fire effluent, as used in BS 6853 (1999). The calculations 96 kg m−3
showed that, for both the rigid polyurethane and the FR GM-31 Farrar et al 1979 14.2
polyisocyanurate, hydrogen cyanide is the major toxicant No details provided Babrauskas et al 1991b 22.0
in smouldering, well-ventilated and under-ventilated flam- NFR GM-30 Levin et al 1983b 38.4
ing. The authors acknowledged that they did not include
isocyanates in their calculations.
Neviaser and Gann (2004) compiled the toxic potency
NFR isocyanurate, GM-41 Farrar et al 1979 11.4
data for a range of materials including a number of fire
retarded and non-fire retarded polyurethane foams. The NFR isocyanurate, GM-43 Farrar et al 1979 5.8
authors compiled toxicological data from a range of pri- NFR GM-29 Farrar et al 1979 11.2
mary online databases and also requests were made to NFR GM-35 Farrar et al 1979 12.1
collect unpublished data that were not publically avail- NFR GM-37 Farrar et al 1979 10.9
able. From this, the library of data was sorted into cat- NFR GM-39, sprayed Farrar et al 1979 16.6
egories of combustion/pyrolysis conditions, material/
product, type of test animal and toxicological endpoint. During flaming combustion, many fire retarded
The authors noted that a large number of the data avail- flexible polyurethane foams showed similar or slightly
able relating to the test conditions were vague or higher toxic potency than the non-fire retarded foams in
completely undefined. In particular, reports that used both well-ventilated and under-ventilated conditions.
non-standard tube furnace apparatus lacked sufficient While limited data were available regarding the flaming
information about the conditions of the experiment and combustion of rigid polyurethane foams, the results were
as such were not included. The data was presented as of a similar scale to those presented by Stec and Hull
material-LC50 values for 30 min exposures with 14-day (2011). While the data presented is a useful compilation
post-exposure of test animals and can be found in of toxic potency data from the available literature before
Tables 10, 11 and 12. 2004, the report does not take into consideration the
Table 11 LC50 values for under-ventilated flaming combustion Table 12 LC50 values for oxidative pyrolysis (Neviaser &
(Neviaser & Gann 2004) Gann 2004)
Material Reference Material-LC50 Material Reference Material-LC50
(30 min + 14 (30 min + 14
day post)/ day post)/
g m−3 g m−3
Flexible polyurethane foam Flexible polyurethane foam
No details provided Babrauskas et al. 18.0 NFR FPU #12 Levin et al 1983a 37.8
1991b
NFR FPU #13 Levin et al 1986 37.0
FR upholstered chairs Barbrauskas et al. 23.0 −3
NFR Foam: 22.3 kg m Braun et al 1990 33.0
with FPUR padding, 1988
cover fabric and a NFR GM-21 Levin et al 1983b 27.8
steel frame
Melamine type foam Babrauskas et al. 8.0
1991b NFR GM-21 Levin et al 1983b 26.6
Melamine type foam Babrauskas et al. 15.0 FR FPU #11 Levin et al 1983a 17.2
with vinyl fabric 1991b FR FPU #14 Levin et al 1983a 40.0
Melamine type foam Babrauskas et al. 15.0 −3
FR Foam: 22.3 kg m Braun et al 1990 23.0
with vinyl fabric 1991b
Rigid polyurethane foam
No details provided Babrauskas et al. 14.0
1991b NFR GM-21 Farrar et al 1979 13.4
conclusions of individual authors, the exact specifics of NFR Foam Farrar & Galster 1980 14.3
the test condition, and the validity of the results. The NFR GM-21: 2 PCF Anderson et al 1983 34.7
data also does not specify the fire retardants used. Over- Rigid polyurethane foam
all, the report provides access to a large pool of data NFR GM-30 Levin et al 1983b 34.0
organised into a material-LC50 and also helps demon- NFR GM-30 Levin et al 1983b 39.6
strate that the large majority of data available is for well-
ventilated tests.
Conclusions NFR Isocyanurate; GM-41 Farrar et al 1979 8.0
The non-flaming decomposition of polyurethanes in air NFR isocyanurate; GM-43 Farrar et al 1979 5.0
or nitrogen can be summarised effectively using a gener- NFR GM-29 Farrar et al 1979 40.0
alised mechanism based on the available literature NFR GM-35 Farrar et al 1979 36.7
(Fig. 9). The mechanisms of decomposition are well
understood and the decomposition products of both
rigid and flexible polyurethane foams are very similar NFR GM-39; sprayed Farrar et al 1979 10.9
at high temperatures. At lower temperatures, decom-
position differs, depending on the composition and During flaming combustion of polyurethane foams,
physical properties of the polymer, although clear the yield of toxicants can be directly related to the fuel/
trends can be identified. A detailed understanding of air ratio, expressed as an equivalence ratio (ϕ). This
the thermal decomposition chemistry of polyurethane results in relatively high yields of CO and HCN dur-
foams is necessary in order to relate the toxicants ing under-ventilated flaming and relatively low yields
generated during both flaming and non-flaming com- during well-ventilated flaming. Test methods, such as
bustion of the polymer to its structure. the steady state tube furnace (ISO/TS 19700) and the
CO and HCN are the main asphyxiants produced dur- controlled atmosphere cone calorimeter (ASTM E 1354),
ing the combustion of polyurethanes and there have facilitate ventilated controlled conditions which give yields
been a large number of studies published regarding their of CO and HCN comparable to those observed in under-
yields. Isocyanates should be considered when assessing ventilated post-flashover compartment fires. The average
the fire toxicity of polyurethane foams, due to their CO yield expected from under-ventilated flaming is
acute irritating effects and chronic effects associated ~200 mg g−1 for polyurethane materials.
with exposure. However, there is very little literature HCN, in particular, contributes significantly to the
available regarding the yields of isocyanates produced by overall fire toxicity of polyurethane foams. Around 10–
the combustion of polyurethane foams. 15 % of the nitrogen in the polymer can be converted
into HCN with some being released in isocyanates, Authors’ contributions

aminoisocyanates and amines in the fire effluent. Add- STM wrote the manuscript and produced all of the images used in figures.
TRH wrote the fire toxicity section of the manuscript. Both authors read and
itionally, HCN yields in both flaming and non-flaming approved the manuscript.
conditions increases with temperature. This can be
explained by the fragmentation of nitrogen containing Acknowledgements
The authors would like to thank Dr. Linda Bengtstrom for her contribution
organics in the flame and in the effluent, as suggested
regarding the toxicity of isocyanates.
by studies of the inert-atmosphere decomposition of
polyurethane materials. HCN yields reported in under- Funding
ventilated conditions vary depending on the composition of STM would like to acknowledge the University of Central Lancashire for
provision of a studentship.
the material; with flexible foams producing less than rigid
foams and polyisocyanurates producing the most overall. Received: 3 February 2016 Accepted: 31 March 2016
The overall toxicity of polyurethane materials followed a
similar trend to their HCN yields; with flexible foams gen-
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McKenna and Hull Fire Science Reviews (2016) 5:3

REVIEW Open Access

The fire toxicity of polyurethane foams

Introduction are joined by a range of functional groups primarily

Fig. 1 The urethane functional group

Isocyanate reactivity isocyanates. Additionally, aromatic isocyanates with

Scheme 3 Reaction of an isocyanate with an amine to produce a urea

Scheme 4 Reaction of an isocyanate with a urea to produce a biuret linkage

Short chains with high functionality results in highly Regeneration of Precursors

Scheme 5 Reaction of a urethane with an isocyanate to produce an allophanate linkage

Scheme 6 Self-addition reaction of two isocyanates to produce a uretidione

Scheme 7 Self-addition reaction of three isocyanates to produce a isocyanurate ring

Scheme 8 Reaction of two isocyanates to produce a carbodiimide

with an increase from 20.8 mg g−1 to 38.0 mg g−1. Simi-

Fig. 7 A polyether polyol (i) and a polyester polyol (ii)

The main toxic combustion products can be divided Asphyxiant gases

Nitrogen oxides Equation 1 Purser model

This equation only relates to lethality, or cause of

Bench-scale methods for generating toxic effluents

Fig. 11 The controlled atmosphere cone calorimeter

Fig. 12 The Steady state tube furnace apparatus, ISO/TS 19700

into HCN with some being released in isocyanates, Authors’ contributions

Polyether Polyurethane Foam Using Both Condensed and Gas-Phase Release

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