Journal Journal of Fire Sciences 2000 456

Journal of Fire Sciences
http://jfs.sagepub.com
Analysis of Fire Gases Released from Polyurethane and Fire-Retarded

Polyurethane Coatings
Sophie Duquesne, Michel Le Bras, Serge Bourbigot, Ren Delobel, Franck Poutch,
Giovanni Camino, Berend Eling, Chris Lindsay and Toon Roels
Journal of Fire Sciences 2000; 18; 456
The online version of this article can be found at:
http://jfs.sagepub.com/cgi/content/abstract/18/6/456
Published by:
http://www.sagepublications.com
Additional services and information for Journal of Fire Sciences can be found at:
Email Alerts: http://jfs.sagepub.com/cgi/alerts
Subscriptions: http://jfs.sagepub.com/subscriptions
Reprints: http://www.sagepub.com/journalsReprints.nav
Permissions: http://www.sagepub.com/journalsPermissions.nav
Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

2000 SAGE Publications. All rights reserved. Not for commercial use or unauthorized distribution.
Analysis of Fire Gases

Released from Polyurethane
and Fire-Retarded
Polyurethane Coatings
SOPHIE DUQUESNE,* MICHEL LE BRAS
AND SERGE BOURBIGOT
Laboratoire de Gnie des Procds dInteractions Fluides RactifsMatriaux
UPRES EA 2698, E.N.S.C.L.-USTL
BP 108, F-59652 Villeneuve dAscq Cedex, France
REN DELOBEL, FRANCK POUTCH
CREPIM, 62-Bruay la Buissire, France
GIOVANNI CAMINO
Dipartimento di Chimica Inorganica e Chimica dei Materiali
University of Torino
Torino, Italy
BEREND ELING, CHRIS LINDSAY AND TOON ROELS

ICI Polyurethanes
Everberg, Belgium
(Received June 7, 2000)
(Revised October 31, 2000)
ABSTRACT : We have investigated the analysis of smoke and gases generated

under various thermal decomposition conditions of polyurethane (PU) and fire
retarded polyurethane coatings. The use of Fourier Transform Infrared
Analysis has allowed the continuous detection of a number of the most
important fire gases. We have shown that the addition of ammonium
*Author to whom correspondence should be addressed.

E-mail: s.duquesne@pop.ensc-lille.fr
456
JOURNAL OF FIRE SCIENCES, VOL. 18 NOVEMBER/DECEMBER 2000

1530-8049/00/06 045627 $10.00/0 DOI: 10.1106/6CRG-Q8VD-PV3G-ELDD
2000 Technomic Publishing Co., Inc.
Analysis of Fire Gases Released from Polyurethane
457
polyphosphate (APP) in PU sharply decreases at the same time the emission of

toxic gases such as CO or HCN, the optical density of smoke, the weight loss and
the formation of soot. Expandable graphite, when added in PU, enables a
decrease in toxic gases in a lower proportion than APP. In addition, we note that
oxidation reactions strongly influence the nature of the combustion gases in
case of fire.
KEY WORDS: flame-retardancy, intumescence, polyurethane, smoke, FTIR.
INTRODUCTION
POLYURETHANES (PU) HAVE been developed into many types and classes
of products with a large variety of properties [1]. Due to the large variety
of isocyanates and polyols which can react together [2], polyurethane
products possess a broad range of properties and have many applications, including foams, elastomers, adhesives and coating [3]. Like the
vast majority of organic materials, polyurethanes are combustible [4].
Consequently, their use can be restricted in buildings or in mass transport applications.
One way to flame retard polymers is to use intumescent systems [56].
Intumescent materials bubble and foam on heating to form a cellular
charred layer on their surface, which protects the underlying material
from the action of heat flux or flame. The accepted mechanism is based
on the charred layer acting as a physical barrier, which slows down heat
and mass transfer between the gas and the condensed phases [7].
Ammonium polyphosphate (APP) is a typical phosphorus-based compound used in intumescent formulations [89], and its performance
when it is incorporated into PU has been previously demonstrated
[1011]. Expandable graphite (EG) is a radically different intumescent
additive that has found use in a number of flame retardant applications
[1213] and its efficiency in PU foam has been largely reported in the
patent literature [1415].
Fire performance of PU/APP and PU/EG coatings in term of LOI
(Limiting Oxygen Index) values versus loading in additive are reported
in Figure 1.
Addition of APP in PU increases the LOI to 44 vol.-%. EG presents
good flame retardancy at low loading levels.
This paper reports the analysis of the gases evolved during the degradation of PU and fire retarded PU coatings. These coatings may be used
to protect several kinds of substrates, particularly plastics. The use of
such a coating represents an alternative approach for improving fire
retardancy of polymers and may eliminate many of the disadvantages

458
SOPHIE DUQUESNE ET AL.
Figure 1. LOI for APP- and EG-based formulations versus additives content.
caused by the incorporation of additives in polymer such as the loss of

mechanical properties, processability, etc.
Conditions chosen for the analysis of gases evolved during thermal
decomposition, ranged from vacuum to oxidising environments and
from constant temperature to high heating rate. As illustrated in Figure
2, pyrolysis and thermo-oxidative degradation are common combustion
processes. Consequently, a comparison of thermal degradation products
from a flame with those from an inert atmosphere can provide an
improved understanding of combustion processes.
Three different thermal decomposition techniques have been used to
Figure 2. Schematic representation of flaming combustion.

459
study polymer degradation gases. These were the thermal volatilisation

analysis, the tubular furnace and the cone calorimeter. Because a burning polymer produces a complex mixture of many gases, Fourier Transform Infrared Analysis (FTIR) seems to be one of the most suitable
methods for obtaining a comprehensive analysis of evolved gases during
thermal degradation or fire [16,17]. It enables the simultaneous determination of a large number of the gas phase components by sampling
from the continuous effluents stream from a fire on thermal degradation
source. These gases include important harmful products from the degradation of PU such as hydrogen cyanide, nitrogen oxides as well as carbon
monoxide and carbon dioxide which are produced from most fires.
EXPERIMENTAL
Materials
Reagents used were polymeric diisocyanate diphenylmethane and
polyester polyol (chemical structure details are not available from the
producer). The PU coatings were obtained by polycondensation of the
isocyanate with the polyol:
The molar ratio NCO/OH was set at two in order to obtain a reticulated network. The study was focused on two fire retardants: ammonium
polyphosphate (APP, (NH4PO3)n, n = 700, Hoechst Hostaflam AP422,
soluble fraction in H2O: < 1 wt.-%) and expandable graphite (EG,
Callotek 500, Graphitwerk Krophfmhl). Expandable graphite is a
Graphite Intercalation Compound (GIC). The graphite structure consists of layers of hexagonal carbon structures within which a chemical
compound (e.g., H2SO4) can be intercalated (Figure 3). EG is prepared
either by oxidation with a chemical reagent [18] or electrochemically
[19,20] in the intercalating acid (i.e., H2SO4, HNO3, etc). The chemical
reaction in the case of H2SO4 is expressed by the following equation:
+ (HSO- )( m - 1)H SO + 1 / 2 H O
24nC + mH2SO4 + 1 / 2 O2 C24n
4
2
4
2
The result is a graphite acid salt, so named because of its ionic nature
in which the positive charge of the oxidised graphite network is balanced

460
Figure 3. Structure of H2SO4 graphite acid salt.
by negatively charged acid anions and includes also acid molecules (as
shown in Figure 3) for H2SO4 GIC [21].
The study has been carried out using 40 wt.-% APP or 15 wt.-% EG
loading in the PU material.
The initial mixing (monomers/additive) was carried out using a Turbo
Turrax mixer (8000 pRad/min4000 rpm). Polyol and isocyanate were
then added together with a velocity of about 1000 pRad/min (500 rpm).
Polycondensation occurred at room temperature.
Thermal Volatilisation Analysis (TVA)
Thermal Volatilisation Analysis (TVA) is a technique developed in the
Chemistry Department of the University of Glasgow by Dr. I.C. McNeill,
which has been very widely applied in various investigations related to
polymer stability and mechanisms of breakdown [22].
TVA experiments involve the measurement of the pressure of substances undergoing transfer from one point to another in an initially

461
Figure 4. Thermal volatilisation analysis.
evacuated system, which is continuously pumped. The experiment provides the rate of volatilisation versus temperature (or time). The basic
layout is presented in Figure 4.
In this study, TVA experiments have been carried out with a heating
rate of 10C/min over the temperature range 20500C. Evolved gases
were trapped using liquid nitrogen and then collected in a quartz cell
before analysis by FTIR using a Perkin-Elmer FTIR 2000 Spectrometer
connected to a Grams Analyst 2000 Perkin Elmer data station.
Tubular Furnace
The tubular furnace method allows the thermal degradation of polymer materials in air and, by using appropriate instrumentation, quantitative analysis of the combustion gases (CO2, CO, HCN, SO2) [23].
Experiments have been carried out at 600C for 20 min. In all cases,
the mass of the sample used was fixed at about 1 g. The samples were
positioned in open porcelain pans placed in a tube. Gases were continuously extracted using a pump (0.12 m3/h).
Two series of experiments have been carried out. In the first (Figure
5), HCN and SO2 were collected in traps (using NaOH and H2O2 respectively). Concentration in solution was then determined using ion chromatography [23]. Specific analysers (nondispersive infrared detectors)
for CO2 and CO were located at the end of the line. In the second series of
experiments, a FTIR spectrophotometer (Nicolet 710C) was used
Figure 5. Schematic diagram of the tubular furnace.

462
on-line, and it has enabled the continuous detection of gas components

in the smoke. The gas cell had a volume of 750 cm3, a 3.77 m path length
and was operated at 650 torr. The sampling line is maintained at 183C.
We have assumed that the partial pressure of combustion products is low
enough to prevent liquid or solid condensation in the sampling line and
in the cell. The FTIR was set to generate one spectrum every 20 seconds.
Cone Calorimeter
For this study, a Nicolet FTIR spectrometer (NICOLET 710C) was
used attached to a cone calorimeter. Samples (sheet of coating: 100
100 3 mm3) were exposed to a heat flux of 50 kW/m2. This flux was chosen because it corresponds to the evolved heat during an enclosure fire
[24]. Fire effluents were extracted at a flow rate of 24 dm3/min. Specific
analysers for CO2 and CO (nondispersive infrared detectors) were
located at the end of the line in order to quantify the concentration of
these gases. A quantitative analysis of smoke opacity was achieved using
a laser photometer. A smoke filter removed soot particles from smoke
and enabled to determine the soot mass after cone calorimeter experiment.
Samples of effluent gases were then extracted using a further tube
from the main extract system at a rate of 8 dm3/min and analysed by
FTIR. A smoke filter removed soot particles from the gas sample before
it reached the FTIR analyser. The sampling line, approximately 4 meters
long, was maintained at 183C in order to avoid condensation. The specifications of the FTIR analysis system were similar to those used for the
tubular furnace (pressure 650 torr, volume 750 cm3, path length 3.77 m).
Infrared Absorption Region
Table 1 summarises the infrared absorption regions for the main gaseous products from the thermal degradation of the polymers. In this
study, spectra were interpreted according to this table.
RESULTS AND DISCUSSION
Thermal Volatilisation Analysis
TVA traces of total gases for PU and FR PU coatings are presented in
Figure 6. In the case of pure PU, volatile products emission begins at
about 250C and the rate of evolution reaches a maximum at about
350C. The main pattern of the TVA trace does not change if EG is added
in PU. However, emission of gases begins at lower temperature (about


Species
HCN
NH3
CO2
CO
NO2
NO
Dioxane
Formaldehyde
H2O
SO2
CH4
Aniline
Absorption bands/cm1
Assignment
Reference
815615
34053210
1200720
18301450
3400-3200
24002250
22502000
16501550
19501750
930840
11801020
30002800
CH bending
CH stretching
N-H out of plane bending
N-H in plane bending
N-H stretching
CO2 asymmetrical stretching vibration
CO stretching
NO2 asymmetrical stretching
NO stretching
COC symmetrical stretching
COC asymmetrical stretching
CH stretching two bands appear (2850 10: sym.
stretching, 2925 10: asym. stretch)
[25]
[25]
[26]
[26]
[25,26]
[27]
[26]
[26]
[26]
[26]
[26]
[26]
1280980
24002300
30502800
18501350
1400-1300
12001100
32002850
15001450
13001250
CH stretching two bands appear (2850 10: sym.

stretching, 2925 10: asym. stretch)
H2O bending
SO2 asymmetrical stretching
SO2 symmetrical stretching
Asymmetrical stretching
N-H in plane bending
C-N stretching
[28]
[28]
[26]
Table 1. IR absorptions of the gaseous products of thermal degradation of polymers and their assignments.
[25]
[26]
[26]
[25,26]
[26]
[26]
463
464
Figure 6. Rate of volatilisation versus temperature trapped at 0C.
200C) which corresponds to the onset temperature of EG (i.e., the

temperature at which a material begins to expand) [29]. The peak corresponding to the exfoliation of EG overlaps with the major step of the
polymer degradation. In the case of PU/APP, the TVA trace shows two
stages of volatilisation: 230320C and 320400C. The degradation of
APP has been previously reported in the literature [30]. Above 200C,
pure APP begins to lose ammonia, resulting in formation of highly condensed polyphosphoric acids. Maximum degradation occurs at higher
temperature than 300C. At temperatures higher than 530C,
polyphosphoric acids may be evaporated and/or dehydrated to P4O10.
This study shows that degradation of the PU/APP system begins at a
lower temperature than degradation of pure polymer and APP suggesting that the polymer and the additive react together as a first step.
The products released in a TVA experiment exist in three main
fractions:
1. Gaseous and volatile liquid products which leave the degradation
zone and pass through the apparatus to the liquid nitrogen trap
2. High temperature boiling products which are volatile at the degradation temperature but which condense on the cooled upper part of the
TVA tube
3. Solid residue of thermal degradation

465
In this paper, we have focussed our attention on the first fraction.

FTIR spectra of the gaseous products of degradation of PU and FR PU
coatings are presented in Figure 7. Using the data in Table 1, it is clear
that carbon dioxide is evolved whatever the formulation. Comparison of
the spectra for PU and PU/EG indicates that products of degradation are
similar. However, as EG decomposes evolving sulphur dioxide, the IR
spectrum of the gases presents an additional peak at 1347 cm1 due to
SO2 compared to pure PU.
In addition, in both cases, peaks at 1133 cm1 and 880 cm1 may be
attributed to 1,4-dioxane possibly produced through the condensation of
diethylene glycol (which might be evolved from a depolycondensation
reactiondegradation of PU begins with scission of the urethane bonds
to yield polyol and isocyanate [10]):
A peak around 1730 cm1 indicates the presence of organic species

including carbonyl C=O (stretching vibration). We also noted the presence of peaks around 2800 and 2970 cm1 which may be attributed to
Figure 7. FTIR spectra of gases trapping at 196C collected after TVA experiments.

466
CH2 or CH3 groups (stretching vibration). However, it was not always

possible to clearly identify gas components. A limitation of the TVA technique concerns the size of the sample which is necessarily small to avoid
diffusion and possible gradient temperature effects [31]. As the mass of
the sample is lower than 200 mg, it is only possible to identify the major
components of the smoke due to the weak intensity of the peaks representing minor components.
In the case of PU/APP, peaks around 950, 1623 and 3328 cm1 may be
attributed to ammonia. Peaks in this spectral region corresponding to
minor products of degradation may be hidden because of the high concentration of ammonia evolved from the degradation of APP.
Tubular Furnace
Results obtained in the first series of the tubular furnace experiments
are presented in Table 2. We have observed that the addition of the fire
retardants used in this study increases the residue mass after the experiment when compared to PU without additive. The residual char mass is
particularly high in the case of PU/APP. A chemical reaction between
the matrix and the additives takes place which results in a stabilisation
of the residue. At least ammonia is evolved at this temperature during
the reaction. The high residual weight (40 wt.-%) may not be then
related to the initial loading of APP in the materials but to a stabilisation
of the carbonaceous material.
It is also of interest to note that APP yields NH3 when degrading,
resulting in basic smoke, whereas EG generates SO2, resulting in acid
smoke formation. In both cases, these gases may dilute the combustible
gases released from the PU degradation and consequently reduce the
flammability of polymer.
We also observed that the addition of FR additives limits the producTable 2. Quantitative analysis of gaseous products
of degradation using tubular furnace method (limits
established according to interlaboratories repeatability tests).
Formulation
FR
(%)
CO
(mg/g)
CO2
(mg/g)
HCN
(mg/g)
SO2
(mg/g)
pH
Smoke
%
Residue
(wt/wt)
PU coating
PU/APP coating
PU/EG coating
0
40
15
250 80
50 20
110 30
650 200
250 80
800 250
14 4
52
93
/
/
62
/
Basic
Acid
1.2
40.0
10.7

467
tion of CO and HCN, which are the main narcotic gases identified in fire
[32].
That the addition of APP decreases carbon dioxide formation compared to pure PU is considered an important finding. By contrast, CO2 is
evolved in large quantities when PU/EG degrades. This may be
explained by the reaction mechanism of degradation of EG, which consists of an oxidation of the carbon layer (C + 2H2SO4 CO2 + 2SO2 +
2H2O) [29].
In summary, the addition of APP or EG clearly reduces the production
of CO, CO2 and HCN evolved when PU degrades. In addition, we note
that PU/EG produced higher yields of toxic gases compared to PU/APP
and that less residual char is formed with PU/EG.
Infrared spectra of the gaseous products of degradation versus time
for PU and FR PU coatings are presented in Figures 8, 9, and 10. Gases
which can be detected in the fire effluent are summarised in Table 3.
For all formulations, we have assumed the presence of hydrogen cyanide. HCN absorbs in several regions, but interferences from other gases
may give difficulties. For example, peaks in the 615815 cm1 wave number region have strong interferences from water and CO2, and the twin
peak in the 32103400 cm1 wave number region may overlap with the
spectra of ammonia.
Figure 8. Infrared spectra of gaseous products of degradation of PU coating versus

time for a sample decomposed at 600C.

468
Figure 9. Infrared spectra of gaseous products of degradation of PU/APP coating

versus time for a sample decomposed at 600C.
Figure 10. Infrared spectra of gaseous products of degradation of PU/EG coating

versus time for a sample decomposed at 600C.

469

Table 3. Volatile products from decomposition of
PU and FR PU coatings from IR analysis.
Presence: Y (Yes), N (No), P (Possible).
Species
HCN
NH3
CO2
CO
NO2
NO
Dioxane
Formaldehyde
H2O
SO2
CH4
PU
PU/APP
PU/EG
Y
N
Y
Y
Y
N
Y
Y
Y
N
Y
P
Y
Y
Y
Y
N
Y
P
Y
N
N
Y
N
Y
Y
P
N
Y
Y
Y
Y
Y
On the spectra of the fire effluents of PU and PU/EG formulations

(Figure 8 and Figure 10), a peak is observed around 715 cm1, and a twin
peak of weaker intensity in the 32103400 cm1 region confirms the presence of HCN in the gases. We also noted that the emission of HCN occurs
throughout the duration of the experiment. For PU/APP, ammonia
absorption hides that from HCN. Consequently, it is difficult to confirm
the presence of HCN in the gaseous products of degradation. However, it
is possible to assume its emission (according to previous analysis) but at
a lower level than in the case of PU and PU/EG formulations.
Ammonia has a distinctive IR spectrum. Moreover, 40 wt.-% loading in
additive for the PU/APP formulation has been employed. The presence
of ammonia is, therefore, clearly observed for this formulation and for
the duration of the experiment.
Carbon monoxide and carbon dioxide may be clearly observed using
FTIR. Carbon monoxide has a highly detailed and strong spectrum in
the 20002250 cm1 region. Carbon dioxide interferes at the higher edge
of its spectral band with a strong band in the 22502400 cm1 wave number region.
Whatever formulation was studied, both of the carbon oxides were
evolved. However, as noted using specific analysers, lower quantities of
CO and CO2 are released in the case of PU/APP formulation compared to
the others studied.
Nitrogen oxide may be evolved when N-containing polymers, such as
PU burn. It was detected in the gaseous products of degradation of the
PU and PU/APP formulations. We also noted that it is evolved in a larger
quantity in the case of PU/APP over the same period that water is also

470
produced in a large quantity. This may be important in terms of fire

retardancy. It is well known that the latent heat of vaporisation of water
tends to reduce the temperature of the fuel resulting in more effective
fire retardancy.
We have assumed that the emission of a large quantity of NO2 is due to
the presence of APP. As previously reported in literature, APP decomposes, leading essentially to the elimination of NH3 and H2O. Ammonia
may then further react with the oxygen of the air to yield nitrogen oxides
and water. On the other hand, it has already been reported that nitrogen
oxides are also formed in the high temperature flames by thermal fixation of nitrogen and oxygen molecules in the air [33]. Nitric oxide was
not found to be present in the effluent whatever the formulation is.
Formaldehyde is clearly detected in PU and PU/EG formulations. In
the case of PU/APP, the spectrum of ammonia overlaps with that of
formaldehyde one over range of wave numbers 9801280 cm1 and with
CO2 in the range 23002400 cm1. However, we have assumed that it is
produced because of the absorbance in the 28003050 cm1 wave number
region.
Sulphur dioxide is produced from expandable graphite. SO2 shows a
relatively broad but weak FTIR spectrum in the 13001400 cm1 wave
number region. It suffers interferences from water absorption. It was
clearly detected in the case of PU/EG during the first part of each experiment (i.e., up to 3 minutes).
Methane and/or higher types of alcane are detected in the case of PU
and PU/EG formulations. This proves that the combustion is incomplete
in such conditions. This is relevant when considering fire retardancy.
The heat generated will be lower if such gases do not burn in a flame.
Finally, we note from the spectra of Figure 8 (PU) and Figure 9
(PU/APP) the presence of a strong band around 1500 cm1. This band
may be attributed to N-H bending in amine and/or amide. Also, we
observed another band in the 12501300 cm1 wave number region
which may be due to the presence of C-N bonds. We have assumed the
presence of aniline in the smoke of PU and PU/APP.
The formation of such species may be explained by the degradation of
the diamine (released from PU degradationPMDI) which leads to the
formation of aniline and formaldehyde [10] as shown in Figure 11. The
presence of PMDI in the smoke may be diverted while no absorption
around 1720 cm1 (C=O) and around 2270 cm1 (N=C=O) are observed
simultaneously on the spectra. It would rather decompose than volatilise. No aniline was detected in the gases released from PU/EG degradation.
We observed that aniline and formaldehyde emissions are particu-


Figure 11. Formation of analine and formaldehyde.
471
472
larly high when APP is added in PU. So, we assume that it is the phosphoric acid, released when APP degrades, which catalyses the reaction of
degradation of diamine.
Cone Calorimeter
Table 4 reports the quantitative analysis of the gaseous products collected when samples are exposed to a heat flux of 50 kW/m2.
The yield of soot is decreased when EG is added to PU, even though it
is still evolved in the same quantity in the case of the PU/APP formulation. Soot is defined as the solid and liquid particles of fullerene structure type in suspension in smoke. The repartition of the soot particles
radii is very large (from 0.2 nm to about 20,000 nm in large agglomerates, i.e., from 4 to about 1015 carbon atoms per particle, as a function of
the temperature) [34]. In our case, only particles with radii higher than
1000 nm will be taken into account.
In addition, the pure PU produced the highest quantity of smoke. The
formation of smoke has to be taken into account when assessing life risks
in fire. The formulations including fire retardant additives show a lower
degree of smoke formation (the quantity decreases by 40% for PU/APP
and by 70% for PU/EG). This decrease should be related, in the case of
PU/APP, to the amount of initial additive in the matrix, but the analyses
with the tubular furnace and the composition of the smoke demonstrate
that the additive and PU interfere. The smoke evolution rates during
burning are presented in Figure 12. The pure PU sample coating
developed a relatively large quantity of smoke during the first part of the
experiment (i.e., < 5 min). Incorporation of EG slightly decreases the
peak of smoke emission. However, smoke is developed over a shorter
period. The addition of phosphorus in the form of APP strongly
decreases the peak of v.s.p. (volatile smoke production), but emission of
smoke occurs during a longer period. This may be explained by the fact
Table 4. Quantitative analysis of gaseous
products and soot using FTIR method.
Formulation
FR
(%)
Weight
Sample
(g)
Residual
Weight*
(%)
CO2**
(%-vol.)
CO**
(mg)
Soot**
(g)
Volume of
Smoke*
(m3)
PU coating
PU/APP coating
PU/EG coating
0
40
15
40
40
35
20
50
30
143
6
89
110
16
120
1.82
1.85
0.74
1.03
0.63
0.31
*After 10 min of experiment.

**After 15 min of experiment.

473
Figure 12. Volume of smoke production versus time for samples exposed to a heat
flux of 50 kW/m2.
that the addition of APP leads to incomplete combustion resulting in an

increasing density of smoke.
In addition, pure PU polymer shows a low char formation (loss of
approximately 80% of its initial weight after 10 min of experiment),
whereas the addition of fire retardants significantly increases the weight
of unburned char.
The emissions of CO and CO2 are significantly decreased when APP is
added to PU. However, in the case of EG, carbon monoxide is still evolved
in relatively large yields. Consideration of the concentration of CO and
CO2 versus time (Figure 13 and Figure 14) shows that the peak of concentration of CO is sharply reduced when EG is added to PU. However,
in the latter part of the experiment, CO is still released in large quantity.
A similar shape curve is observed for the pure polymer. CO2 exhibits its
peak value at the same time as CO, and it is not released until 5 min into
the experiment. Consequently, in the latter stages of the experiment,
i.e., when the flaming combustion has stopped, combustion tends to be
incomplete. During this period, we observe glowing combustion, i.e.,
combustion of the material in the solid phase without flame but with
emission of light from the combustion zone.
Figures 15, 16 and 17 show the infrared spectra versus time of the fire
effluents collected during the degradation of PU and FR PU coatings;
Table 5 summarises the gases which can be detected in the fire effluents.
It should be pointed out that the fire effluents in the case of cone calorim-

474
Figure 13. CO (ppm) versus time for samples exposed to a heat flux of 50 kW/m2.
Figure 14. CO2 (vol.-%) versus time for samples exposed to a heat flux of 50 kW/m2.

475
Figure 15. Infrared spectra of gaseous products of degradation of PU coating versus

time for a sample exposed to a heat flux of 50 kW/m2.
Figure 16. Infrared spectra of gaseous products of degradation of PU/APP coating

versus time for a sample exposed to a heat flux of 50 kW/m2.

476
Figure 17. Infrared spectra of gaseous products of degradation of PU/EG coating versus time for a sample exposed to a heat flux of 50 kW/m2.
eter experiments were diluted considerably compared to the tubular furnace studies.
We have noted that in the case of PU (Figure 15) and PU/EG (Figure
17), the spectra are similar. CO2, CO and H2O are the main gases of the
fire effluents. Because of high extraction flow with a consequent dilution
of the gases by the air, minor products may not be easily detected. For
Table 5. Volatile products from decomposition of

PU and FR PU coatings from IR analysis.
Presence: Y (Yes), N (No), P (Possible).
Species
HCN
NH3
CO2
CO
NO2
NO
Dioxane
Formaldehyde
H2O
SO2
CH4
PU
PU/APP
PU/EG
P
N
Y
Y
N
N
N
N
Y
N
N
P
Y
Y
Y
P
N
N
N
Y
N
N
P
N
Y
Y
N
N
N
N
Y
P
N

477
the PU/APP formulation, we observe additional peaks due to the emission of NH3, which also may be due to the presence of NO2. As observed
for tubular furnace experiments, we also note the presence of peaks
around 1500 and 1270 cm1. This confirms the catalytic action of the
phosphoric acid released from APP on the reactions during the degradation of the polymer.
DISCUSSION AND CONCLUSION

In this work, we have studied the gas phase thermal decomposition
products from fire retardant polyurethane coatings under several conditions. Good fire retardant performance is obtained when ammonium
polyphosphate or expandable graphite are incorporated in PU coating.
This study shows that FTIR is a powerful analytical tool for determining the gas phase composition during thermal degradation or during
burning. We have determined and simultaneously quantified most of the
important fire gases: carbon monoxide, carbon dioxide, hydrogen cyanide, sulphur dioxide, nitrogen oxides, formaldehyde and some hydrocarbons. We have also obtained information about the nature of
additional components in the smoke (for instance ammonia, amine,
etc.), and consequently, we have a better understanding of the mechanism of degradation of the materials.
Additionally, we have noted that the presence of flame retardant in
PU decreases significantly the emission of toxic gases such as HCN and
CO during the degradation of the polymer. The presence of APP also
increases the amount of residual char. Moreover, smoke and soot are
sharply decreased. We have also observed that the nature of the released
gases is similar for PU and PU/EG coatings, while PU/APP leads to a
more complex mixture of gases.
Finally, comparison of the gas phase obtained during pyrolysis and
thermo-oxidative degradation has demonstrated the importance of the
oxidation reactions in the flame and/or in the condensed phase. TVA
experiments, which occur under vacuum, have given information about
the volatile pyrolysis products. Pyrolysis is defined as irreversible
chemical decomposition of material due to an increased temperature
without oxidation [32]. It is generally accepted that pyrolysis accounts
for thermal degradation of the surface of the polymer. We observed that
the gas phase products differ if the degradation occurs in air (tubular
furnace) or in vacuum (TVA). Consequently, even if pyrolysis is a
well-recognised and normal process of the flaming combustion of polymers, surface oxidation and/or oxidation reactions in the air are also of

478
great importance. We have noted that gaseous products are similar for
tubular furnace and cone calorimeter experiments. Cone calorimeter
enables a simulation of some real fire types (well-ventilated fires). As a
consequence, the gas phase mechanism deduced from thermo-oxidative
degradation analysis is close to what occurs in some fires.
REFERENCES
1. Woods, G. 1990. The ICI Polyurethanes Book-2nd ed., ICI Polyurethanes
and John Wiley & Sons Pub., pp. 16.
2. Hatat, D. 1995. Monographies: Polyurthannes, in Techniques de
lingnieur, Volume AM2, A 3 425, pp. 1-23.
3. Kirk, R.E, Othmer, D.F. 1997. Urethane Polymers, in Encyclopedia of
Chemical Technology, Vol. 24, a Wiley-Interscience Pub., pp. 695725.
4. Papa, A.J. Flame-Retarding Polyurethanes, in Flame Retardancy of Polymeric Materials, Vol. 3, Kuryla, W.C. and Papa, A.J. Ed., Marcel Dekker Inc.
Pub., pp 17.
5. Vandersall, H.L. 1971. Intumescent Coating Systems, Their Development
and Chemistry, J. Fire & Flammability, 2:97140.
6. Camino, G. 1985. Etude du mecanisme dignifugation dadditifs
intumescents pour les polymres in Actes du Premier Colloque
Francophone sur lignifugation des Polymres, J. Martel ed., Saint Denis,
France, pp. 3641.
7. Bourbigot, S., Le Bras, M., Delodel, R., Decressain, R. and Amoureux, J.P.
1996. Synergistic effect of zeolite in an inumescence process : Study of the
carbonaceous structures using solid-state NMR, J. Chem. Soc., Faraday
Trans., 92(1):149158.
8. Levchik, S.V., Costa, L. and Camino, G. 1993. Effect of Ammonium
Polyphosphate on Combustion and Thermal Degradation of Aliphatic Polyamides, Makromol. Chem., Macromol. Symp., 74:9599.
9. Siat, C., Bourbigot, S. and Le Bras, M. 1997. Structural Study of the Polymer Phases in Intumescent PA6-EVA-FR Additive Blends, in Recent
Advances in Flame Retardancy of Polymeric Materials, Vol.7, M. Lewin ed.,
BCC Co. Pub., Norwalk, pp. 318326.
10. Grassie, N. and Zulfiqar, M. 1978. The effect of the fire retardant ammonium polyphosphate, on the thermal degradation of a polyurethane, in
Developments in polymer stabilisation, Vol. 1, G. Scott ed., Applied Science
Pub., 197217.
11. Bugajny, M., Le Bras, M., Bourbigot, S., Poutch, F. and Lefebvre, J.M. 1999.
Thermoplastics Polyurethanes as Carbonisation Agents in Intumescent
Blends. Part 1: Fire Retardancy of Polypropylene/Thermoplastic Polyurethane/Ammonium Polyphosphate Blends, J. of Fire Sciences, 17:494513.
12. Krassowski, D.W., Hutchings, D.A. and Qureshi, S.P. 1996. Expandable
Graphite Flake as an Additive for a new Flame Retardant Resin, Fire
Retardant Chemicals Association, Fall Meeting, Naples, Florida, pp.
137146.

479
13. Okisaki, F. 1997. Flamecut GREP Series New Non-halogenated

Flame-Retardant Systems, Fire Retardant Chemicals Association, Spring
Meeting, San Francisco, California, pp. 1124.
14. Heitmann, U., 1992. Verfahren zur Herstelung eines flammwidrigen
elastischen Polyurethan-Weichschaumstoffes, European Patent EP 0 450
403 A3.
15. Bell, R.W.H., Flexible Flame-Retardant Polyurethane Foams, GB 2 168
706 A.
16. Paul, K.T. 1995. Use of FTIR to Analyse Fire Gases from Burining Polyurethane Foams, Proceedings of the Cellular Polymers II Conference,
Conventry, UK
17. Pottel, H. 1996. Quantitative Models for Prediction of Toxic Component
Concentrations in Smoke Gases from FTIR Spectra, Fire and Materials,
20:273291.
18. Kang, F., Zhang, T.Y., Leng, Y. 1996. Influence of H2O2 on synthesis of
H2SO4-GICs, J. Phys. Chem. Solids, 57(6-8):889892.
19. Kang, F., Leng, Y. and Zhang, T.Y. 1996. Electrochemical synthesis of sulfate intercalation compounds with different electrolyte concnetrations, J.
Phys. Chem. Solids, 57(6-8):883888.
20. Kang, F., Zhang, T.Y. and Leng, Y. 1997. Electrochemical behavior of
graphite in electrolyte of sulfuric and acetic acid, Carbon, 35(8):11671173.
21. Zabel, H., Solin, S.A. ed. 1990. Graphite Intercalation Compounds II.
Springer-Verlag Pub., pp. 145.
22. McNeill, I.C. 1977. The Application of Thermal Volatilisation Analysis to
Studies of Polymer Degradation, in Developments in Polymer Degradation,
Vol1, Grassie, N., ed., Applied Science, London, pp. 4365.
23. Essais de Comportement au feuAnalyse de gaz de pyrolyse et de combustion Mthode au four tubulaire. 1986. Norme franaise NF X 70-100,
afnor, Paris ed.
24. Babrauskas, V.1982. Development of Cone Calorimetera bench scale
rate of heat release based on oxygen consumption, NBS-1R 82-2611, US
Ntl. Bur. Stand.
25. Bair, E.D. 1962. Introduction to Chemical Instrumentation. McGraw-Hill
Book Company Pub., pp. 3645.
26. Kriss-Eross, K. 1976. Analytical Infrared Spectroscopy, in Comprehensive Analytical Chemistry, Svehla, G., ed., Elsevier Scientific Pub., Vol.6,
pp211386.
27. Fleming, I. and Williams, D.H. 1966. Spectroscopic Methods in Organic
Chemistry. Sykes, P., ed., McGraw Hill Publishing Company Limited London, pp. 4077.
28. Georgia State Crime Lab Sample Library.
29. Camino, G., Duquesne, S., Delobel, R., B. Eling, C. Lindsay and T. Roels.
2000 Mechanism of Expandable Graphite Fire retardant Action in
Polyurethanes, American Chemical Society, Washington.
30. Delobel, R., Le Bras, M., Ouassou, N., Alistiqsa, F. 1990. Thermal Behaviours of Ammonium Polyphosphate-Pentaerythritol and Ammonium
Pyrophosphate-Pentaerythritol Intumescent Additives in Polypropylene

480
Formulations, J. Fire Sciences, 8:85108.

31. Still, R.H. 1977. The use and abuse of thermal methods of stability assessment, in Developments in Polymer Degradation, Vol. 1, Grassie, N., ed.,
Applied Science, London, pp. 141.
32. Elomaa M., Sarvaranta L., Mikkola E., Kallonen R., Zitting A., Zevenhoven
C. A. P and Hupa M. 1997. Combustion of Polymeric Materials, Critical
Reviews in Biochem. and Molecular Biol., 27(3):137197.
33. Herrigton, R.M.. 1979. The rate of heat, smoke and toxic gases release from
polyurethane foams, J. of Fire and Flammability, 10:308325.
34. Le Bras, M., Bourbigot, S. and Price, D. 2001. International Plastics Flammability Hanbook, 3rd Ed, Troitzsch, J. ed., Hanser Pub., New York, in
Press.
BIOGRAPHIES
S. Duquesne
Sophie Duquesne received her Ingenieur degree in chemical engineering from Ecole Nationale de Chimie de Lille (ENSCL) in 1998, and
joined the Laboratoire de Gnie des procds dInteraction Fluides
Ractifs-Matriaux (GPRIM) to prepare her French Diplme
dEtudes Approfondies s Spectrochemistry, from Lille University. Her
research concerned the elaboration of new flame retarded coatings and
the comprehension of the mechanism of formation of the intumescence
phenomenon by infrared and solid NMR. From 1998, she prepares her
Ph.D. in spectrochemistry in the same field of research in both the Lille
and the Turino laboratories. Also included are studies of the modeling of
heat transfer in the intumescent coatings during the combustion of the
material taking into account the kinetic and the chemistry of
degradation.
M. Le Bras
Michel Le Bras received his French Doctorat en Chimie Structurale
in 1977 and Doctorat s Sciences Physiques in 1997 from Lille University. He joined ENSCL in 1979 as an Ingnieur de Recherches. His research interests were originally the interaction between gases and
reactive surface including corrosion and heterogeneous catalysis process. From 1989, he directed students and lecturers in research dealing
with thermal degradation and fire retardancy of polymeric material. He
studied most precisely protection via an intumescent process, with a particular interest in the comprehension of the synergistic effects and now

481
studies new intumescent FR materials in which polymers play the part

of the carbonization agents.
S. Bourbigot
Serge Bourbigot received his French Ingenieur degree in chemical
engineering from Ecole Nationale de Chimie de Lille (ENSCL) in 1990
and his Ph.D. in spectrochemistry from the University of Lille in 1993.
He joined GPrIM/ENSCL as Matre de Confrences (lecturer) in
1993. His research interests included the fire-retardancy processes of
resins, especially thermoplastics. In 1999, he received a professorship in
Ecole Nationale Suprieure des Arts et Industries Textiles (ENSAIT).
His research interests include the engineering of textile and fibers. He
studies the process and the properties (including flame retardancy) of fibers and fabric (chemical, mechanical and physical ones).
R. Delobel
Ren Delobel received his French Doctorat es Sciences Physiques in
1983 from Lille University. He joined ENSCL as Professor in Hazards
Evaluation. His research interests have included the formulations and
the studies of catalytic systems. He is the director of the ENSCLs
laboratory and is responsible for a Groupement dIntrt Public: Research Center for the study on Fireproofing Processes of Materials (Centre de Recherche et dEssai sur les Procds dIgnifugation des
Matriaux).
F. Poutch
Franck Poutch received his French Ingnieur degree in industrial
chemistry from Conservatoire National des Arts et Mtiers de Lille in
1997. Now, he manages the Centre de Recherche et dIgnifugation des
Matriaux (CREPIM) in Bruay-la-Buissire, that works on the fire
retardancy of polymers, mainly thermoplastic and cellulose-based materials.
G. Camino
Giovanni Camino graduated in Chemistry in 1966 at the University of
Torino, Italy, where he carried out his research work first as a member of
staff of the Italian National Research Council and as Associate Professor
of Macromolecular Chemistry since 1987. His research interests covered

482
polymerisation mechanisms initially and since 1975 mechanisms of degradation and stabilisation of polymer materials. In particular, he began
studies in thermal degradation and fire retardant mechanisms during a
stage in 1975 at the University of Glasgow, Scotland, with professor Norman Grassie. His area of interest has further broadened to include thermal and photooxidation, ageing of composites. He has published about
180 papers and some chapters in books.
B. Eling
Berend Eling has been involved in the polyurethanes industry since
1984, when he joined ICI after receiving his Ph.D. in polymer chemistry
from the University of Groningen (NL). In 1994, he received a scientific
ladder position as senior PU scientist. During his industrial career he
has been involved with several fundamental aspects of polyurethane
chemistry and physics and the development of novel and improved
PU-based products. Currently his main interest is in the area of PU coatings and adhesives. In 1999 the ICI-Polyurethanes division was acquired
by Huntsman Corporation.
C. Lindsay
Chris Lindsay obtained his degree (1986) and Ph.D. (1990) in Chemistry from the University of Sheffield, England. He joined ICI as a Senior
Research Scientist in November 1989 subsequently worked on the research and development of a broad range of new polymeric materials including polyolefins, acrylics, polyimides and polyurethanes. In 1999, Dr.
Lindsay transferred to Huntsman Polyurethanes to take up a role to develop novel new polyurethane materials based on state of the art polymer science concepts.
T. Roels
Toon Roels received his PhD. in Polymer Chemistry and Physics from
the University of Leuven, Belgium. He joined Huntsman Polyurethanes
in 1997 as a research scientist in the Rigid Foam Section, Construction
Group and moved in early 2000 to the Elastomers R&D Section.


Journal Journal of Fire Sciences 2000 456

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Journal Journal of Fire Sciences 2000 456

Hochgeladen von

Copyright:

Verfügbare Formate

Journal of Fire Sciences

Analysis of Fire Gases Released from Polyurethane and Fire-Retarded

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases

BEREND ELING, CHRIS LINDSAY AND TOON ROELS

ABSTRACT : We have investigated the analysis of smoke and gases generated

*Author to whom correspondence should be addressed.

JOURNAL OF FIRE SCIENCES, VOL. 18 NOVEMBER/DECEMBER 2000

Analysis of Fire Gases Released from Polyurethane

polyphosphate (APP) in PU sharply decreases at the same time the emission of

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

caused by the incorporation of additives in polymer such as the loss of

Figure 2. Schematic representation of flaming combustion.

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

study polymer degradation gases. These were the thermal volatilisation

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

Figure 3. Structure of H2SO4 graphite acid salt.

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

Figure 4. Thermal volatilisation analysis.

Figure 5. Schematic diagram of the tubular furnace.

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

on-line, and it has enabled the continuous detection of gas components

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

CH stretching two bands appear (2850 10: sym.

Analysis of Fire Gases Released from Polyurethane

SOPHIE DUQUESNE ET AL.

Figure 6. Rate of volatilisation versus temperature trapped at 0C.

200C) which corresponds to the onset temperature of EG (i.e., the

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

In this paper, we have focussed our attention on the first fraction.

A peak around 1730 cm1 indicates the presence of organic species

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

CH2 or CH3 groups (stretching vibration). However, it was not always

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

Figure 8. Infrared spectra of gaseous products of degradation of PU coating versus

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

Figure 9. Infrared spectra of gaseous products of degradation of PU/APP coating

Figure 10. Infrared spectra of gaseous products of degradation of PU/EG coating

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

On the spectra of the fire effluents of PU and PU/EG formulations

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

SOPHIE DUQUESNE ET AL.

produced in a large quantity. This may be important in terms of fire

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Figure 11. Formation of analine and formaldehyde.

SOPHIE DUQUESNE ET AL.

*After 10 min of experiment.

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007

Analysis of Fire Gases Released from Polyurethane

that the addition of APP leads to incomplete combustion resulting in an

Downloaded from http://jfs.sagepub.com by naian liu on February 15, 2007