Combustion and Flame 159 (2012) 1016–1025

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Combustion and Flame

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c o m b u s t fl a m e

Stirred reactor calculations to understand unwanted combustion

enhancement by potential halon replacements q
Gregory T. Linteris a,⇑, Donald R. Burgess b, Fumiaki Takahashi c, Viswanath R. Katta d,
Harsha K. Chelliah e, Oliver Meier f
a
Fire Research Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8665, USA
b
Chemical and Biochemical Reference Data Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8320, USA
c
Case Western Reserve University, Cleveland, OH 44106, USA
d
Innovative Scientific Solutions, Inc., Dayton, OH 45440, USA
e
University of Virginia, Charlottesville, VA 22904, USA
f
The Boeing Company, Seattle, WA 98124, USA

a r t i c l e i n f o a b s t r a c t

Article history: Several agents are under consideration to replace CF3Br for use in suppressing fires in aircraft cargo bays.
Received 4 March 2011 In a Federal Aviation Administration performance test simulating the explosion of an aerosol can, how-
Received in revised form 20 September ever, the replacements, when added at sub-inerting concentrations, have all been found to create higher
2011
pressure rise than with no agent, hence failing the test. Thermodynamic equilibrium calculations as well
Accepted 22 September 2011
Available online 7 November 2011
as perfectly-stirred reactor simulations with detailed reaction kinetics, are performed to understand the
reasons for the unexpected enhanced combustion rather than suppression. The high pressure rise with
added C2HF5 or C3H2F3Br is shown to be dependent upon the amount of added agent, and can only occur
Keywords:
Fire suppression
if a large fraction of the available oxidizer in the chamber is consumed, corresponding to stoichiometric
Flame inhibition proportions of fuel, oxygen, and agent. Conversely, due to the unique stoichiometry of CF3Br, this agent is
CF3Br predicted to cause no increase in pressure, even in the absence of chemical inhibition. The stirred-reactor
C2HF5 simulations predict that the inhibition effectiveness of CF3Br is highly dependent upon the mixing con-
Halon replacements ditions of the reactants (which affects the local stoichiometry and hence the overall reaction rate). For
Cargo-bay fire suppression C2HF5, however, the overall reaction rate was only weakly dependent upon stoichiometry, so the fuel–
oxidizer mixing state has less effect on the suppression effectiveness.
Published by Elsevier Inc. on behalf of The Combustion Institute.

1. Introduction
Because of its destruction of stratospheric ozone, production of
the effective fire suppressant CF3Br has been banned by the Mon-
treal Protocol. Although a critical-use exemption has been granted
to the aviation industry for use of recycled halon in cargo bay fire
suppression, the European Union requires replacement of halon in
new design aircraft by 2018, and in existing aircraft by 2040. Sev-
eral replacements have been proposed, but they have all been
found to produce enhanced burning in the FAA Simulated Aerosol
Can test [1], and hence they fail FAA’s Minimum Performance Stan-
dard [2]. In particular, C2HF5, C3H2F3Br, and C6F12O all produce
higher peak pressures in a simulated cargo bay as compared to
no added agent, when they are added at concentrations less than
that required to completely suppress the explosion. (Names and
q
Official contribution of NIST, not subject to copyright in the United States.
⇑ Corresponding author. Fax: +1 301 975 4052.
E-mail address: linteris@nist.gov (G.T. Linteris).
chemical formulas are listed in Table 1.) The agent CF3Br, at sub-
suppressing concentrations, does not cause the overpressure.
The Aerosol Can Test [1] simulates the situation in which a fire
in an aircraft cargo bay container heats an aerosol can (e.g., hair
spray) causing it to burst, creating an explosion. In the test, a
heated container at about 16 bar, releases its contents (propane,
ethanol, and water) as a two-phase impulsive spray via a fast-
acting valve. A continuous DC arc across electrodes located about
1 m downstream of the valve ignites the mixture. The fireball
expands into the chamber atmosphere of ambient air and water
vapor and premixed suppressant, and the temperature and
pressure in the chamber increases (over a time on the order of a
second). During each test, instruments record the pressure, tem-
perature, visual images, and concentrations of agent and oxygen.
Unfortunately, when added at sub-inerting concentrations, the
final pressure rise in the chamber with any of the halon replace-
ment agents is higher than in the absence of agent. The agent
C2HF5, added at a volume fraction of 13.5%, suppressed the explo-
sion; however, when added at volume fractions of 6.2%, 8.9%, and
11.0%, the peak pressure rise was about 3.6 bar, or about twice that

0010-2180/$ - see front matter Published by Elsevier Inc. on behalf of The Combustion Institute.
doi:10.1016/j.combustflame.2011.09.011
 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025
Table 1
Chemical names of compounds of interest.
Formula Trade name Common name
CF3Br Halon 1301 Bromotrifluoromethane
C2HF5 HFC-125 Pentafluoroethane
C3H2F3Br 2-BTP Bromotrifluoropropene
C6F12O Novec 1230, FK-5-1- Heptafluoroisopropyl pentafluoroethyl
12 ketone
with no added suppressant (1.8 bar). With C3H2F3Br, volume frac-
tions of 3% or 4% both gave a pressure rise of 4.3 bar, and volume
fractions of 5% or 6% gave a pressure rise of about 6.7 bar. With
C6H12O, a volume fraction of 4.2% gave a pressure rise of 4.5 bar,
and above that volume fraction (or sometimes at 4.2% itself) the
over pressure was suppressed. In contrast, addition of CF3Br at a
volume fraction of about 3.8% suppressed the explosion, and 2.5%
CF3Br, the pressure rise was only 0.28 bar. (For reference, uncon-
fined tests without suppressants create a 3.4 m diameter fire ball
[3]). The goal of the present work is to understand the reasons
for the higher pressure rise in the FAA aerosol can test with
C2HF5 or C3H2F3Br (at sub-inerting concentrations), and the lack
of this effect with CF3Br.
2. Background
Enhanced combustion in the presence of fire suppressants has
been observed in previous work. A promotion effect has been
shown for halogenated hydrocarbons in shock-tube ignition stud-
ies for some fuels and conditions. For example, it is known that
the H2–O2 mixture can be sensitized by HBr [4–6] and HCl [4], with
promotion under some conditions and inhibition under others.
Moen et al. [7] performed experiments and modeling on the influ-
ence of CF3Br, CF4, and CO2 on the detonability of ethane–air and
ethane– and hydrogen–oxygen mixtures, and found that the inhi-
bition ability of CF3Br was greatly reduced as compared to flame
inhibition, and that CF3Br was a sensitizer for some situations. Sim-
ilarly, Babushok et al. [8] computationally studied the ignition de-
lay of hydrocarbons (H2, CH4, CH3OH, and C2H6) and air with
various halogenated fire suppressants (Br2, HBr, CH3Br, CF3Br,
and CF3H), and also found both promotion or inhibition of the igni-
tion. The varying behavior was complex, likely depending upon
subtle changes to the kinetic pathways as the pressure, tempera-
ture, or mixture composition change.
Wider flammability limits in the presence of halogenated com-
pounds have also been reported. Saito et al. [9] conducted flamma-
bility limit experiments in a tubular flame of premixed
hydrocarbon (methane or propane) and air, with added CF3Br,
CF3H, C3HF7, or C4F10. The traditional fuel–air concentration limits
[10] were determined as a function of agent concentration. With
addition of CF3Br, both the rich and lean limits narrowed steeply
(the mixture became less flammable); whereas with addition of
various hydrofluorocarbons (HFCs), the rich limit narrowed less
steeply, and the lean limit sometimes widened (the mixture be-
came more flammable). These results confirmed the ignition tests
of Moore et al. [11] performed in a spherical combustion chamber,
also with premixed reactants. Recently, Kondo et al. [12] measured
the flammability limits of C2HF5 for spark-ignited premixed gases
in a glass flask [13]; fuels were methane, propane, propylene,
methyl formate, and HFC-152a (1,1-difluoroethane, CF2H–CH3),
with dry air. The addition of the agent C2HF5 narrowed the rich
limit, roughly linearly, up to the inertion point. Conversely, the
lean limit was widened for all fuels, with the order of ranking:
C3H6 < C3H8 < HCOOCH3 < C2H4F2  CH4 (i.e., largest widening of
the lean limit occurred for the fuels with higher H/C ratio). Hence,
these experiments also showed an enhance burning of the fuels
caused by C2HF5 under fuel-lean conditions.
1017
Systematic name Structural formula
Bromotrifluoromethane BrCF3
1,1,1,2,2-Pentafluoroethane CF3  CHF2
2-Bromo-3,3,3-trifluoro-1-propene CH2 = CBrCF3
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3- CF3CF2C(=O)CF(CF3)2
pentanone
Using a constant volume combustion device, Shebeko et al. [14]
studied the effect of various halogenated hydrocarbons on the
combustion of methane– and hydrogen–air mixtures. The flamma-
bility limits generally narrowed with addition of the agents; how-
ever, for C4F8 addition to CH4–air flames, the lean limit widened,
and for C2HF5 or C2F5Cl addition to CH4–air flames, the lean limit
was nearly unchanged. That is, for a CH4–air flame at the lean limit,
a C2HF5 mass fraction of 30% had essentially no effect on the
flammability.
In addition to the flammability limits, the pressure rise, as well
as the rate of pressure rise were also used by Shebeko et al. [14] to
illustrate the promoting effect of the halogenated fire suppressant
for some conditions. For example, when added to lean H2–air
flames, C2HF5 increased the maximum pressure rise at any concen-
tration (up to the extinction point). Further, C4F8 (perfluorocyclob-
utane) addition increased the maximum pressure rise for both lean
and rich H2–air flames. This lack of kinetic inhibition was even fur-
ther substantiated for the agent C4F10 when added to CH4–air
flames, for which even the rate of pressure rise was higher with
agent added up to a volume fraction of 4%.
In experiments with high-speed turbulent flames in a detona-
tion/deflagration tube, Grosshandler and Gmurczyk [15–18] ob-
served more vigorous combustion with CF3I or CF3Br, or various
hydrofluorocarbon inhibitors, while using either propane or ethyl-
ene as fuels. For some conditions, the premixed addition of the hal-
ogenated agent to the air stream increased both the deflagration/
shock propagation rate as well as the pressure ratio across the shock.
The results varied with fuel type, stoichiometry, agent type, and the
presence or absence of turbulence-inducing spirals.
In tests with co-flow diffusion flames, halogenated hydrocar-
bons added to either the fuel or air stream have been shown to
increase total heat release. Holmstedt et al. [19] reported that
HFC-227ea (C3HF7) or HFC-134a (C2H2F4) added to the fuel
(propane) stream of a turbulent jet burner increased the total heat
release, by a factor of 2 and 3.8, respectively, for concentrations
just below that required for extinguishment of the flame. Similarly,
Katta et al. [20] found that CF3H added to the oxidizer stream in a
methane–air cup-burner experiment increased the total heat
release.
Increased pressure can also make HFC–air mixtures more flam-
mable. In a survey paper, Ural [21] noted that while halogenated
hydrocarbons are often considered to have no or low flammability
potential, some have been shown to become flammable at elevated
pressure. In a recent study, Kondo et al. [22] measured the rich and
lean flammability limits of HFC-32 (CH2F2) and HFO-1234yf
(C3H2F4) at pressures of 101–2000 kPa. They found that in general,
at increased pressure, the lean flammability limit was relatively
unchanged, while the rich limit widened significantly.
In large-scale tests, Mawhinney et al. [23] found that applica-
tion of water mist to a fire caused unwanted accelerated burning,
which they believed was due to fluid–dynamic enhancement of
the burning. Hamins et al. [24] reviewed previous work on en-
hanced burning with application of fires suppressants, and also
concluded that the enhanced combustion was due to more rapid
mixing of fuel vapor with air, from the combined effects of en-
hanced turbulent mixing and more vigorous liquid fuel atomiza-
tion from agent jet impingement.
1018 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025

While the possibility of enhanced flammability in the presence determined based on the value of g and the specified volume frac-
of HFC fire suppressants has been described in the work presented tion of each component.
above, no analyses were performed in those investigations to The initial inhibitor volume fraction in the oxidizer gases was
understand why promotion occurred. More typically, HFC agents varied from zero to 13.5% for C2HF5, 6%, for C3H2F3Br, and 5% for
act as fire suppressants, and based on previous work [25–27], CF3Br, corresponding to approximately the maximum amount
C2HF5 would be expected to extinguish—or at least weaken—the added in the FAA tests [1,33]. The fraction of the chamber volume
FAA aerosol can test explosions. In previous work [28], an analysis involved in the combustion, g, was varied from about 0.23–1.00.
based on equilibrium thermodynamics was used to gain insight
into the behavior of the agents C2HF5, C3H2F3Br, and CF3Br in the 3.2. Equilibrium thermodynamics
FAA tests. The analyses were able to predict the experimental pres-
sure rise for addition of C2HF5 or C3H2F3Br at sub-extinguishing The equilibrium conditions of the aerosol can test were calcu-
volume fractions (0–11.2% and 0–6%, respectively). The enhanced lated using both the STANJAN-III program of Reynolds [34], and
combustion with addition of agent to the oxidizer was shown to CEA2 of Gordon and McBride [35]; the two codes gave results very
be due to the higher heat release, caused by involvement of close to each other. The calculations were performed over the wide
increasing fractions of the chamber volume of oxidizer. Nonethe- range of initial conditions described above. Constant enthalpy, con-
less, for CF3Br at all concentrations, and C2HF5 at its suppression stant pressure solutions were obtained, as described in Ref. [28].
volume fraction (13.5%), the pressure rise was less than predicted
by equilibrium thermodynamics, possibly due to kinetic limita- 3.3. Kinetic mechanism
tions in the rate of energy release caused by addition of these
chemically acting agents [29–32]. Hence, it is of interest to exam- A kinetic mechanism to describe the chemical inhibition of the
ine the kinetic behavior of the aerosol can test fuel with air and aerosol can test fuel (propane, ethanol, water) with the HFC and
added agent (C2HF5 or CF3Br). Because of the distributed nature bromine-containing species was assembled from sub-mechanisms
of the explosively dispersed fuel-agent–air mixtures in the FAA available in the literature. For the hydrocarbon mechanism, an
tests [1], perfectly-stirred reactor (PSR) calculations were em- optimized model for ethylene oxidation proposed by Wang and
ployed, as described below. While the conditions in the FAA test co-workers was employed [36,37], that included 111 species and
are likely to include more non-premixed or partially premixed 784 elementary reactions. This model has been optimized by con-
structure (due to the fuel-rich core), premixed stirred reactor cal- sidering experimental ignition delay and species profiles data from
culations nonetheless seem to be a reasonable next step in com- shock tubes, laminar flame speeds, species profile data from flow
plexity (after the equilibrium calculations), that will provide reactors, and species profile data from flat flames. To this mecha-
some insight into the relevant kinetic limitations. nism, more detailed reactions of ethanol were added (5 species
and 36 reactions), as proposed by Dryer and co-workers [38–40].
3. Numerical methods For the reactions of the hydrofluorocarbons (HFCs) in hydrocarbon
flames, the NIST HFC mechanism was used [41,42]. Subsequent up-
3.1. Initial conditions dates to that mechanism were made by NIST workers, as noted
L’esperance et al. [43]. Other changes to the NIST HFC mechanism
The volume fraction of agent in the oxidizer Xinh, is a variable. were made in the present work based on recent experimental mea-
The turbulent mixing during the aerosol release makes specifica- surements and theoretical calculations [44–50] as listed in Table 2.
tion of the oxidizer–fuel ratio near the flame difficult, so calcula-
tions are performed for a range of fuel–oxidizer ratio. However,
because the oxidizer consists of both air and agent (which is also Table 2
Reaction rate modifications as suggested by Saso et al. [44], Takahashi and co-workers
a reactant), the oxidizer is partially premixed. Presentation of the [45,46], Vetters (for T Ü 330 K) [47], Fernandez and Fontijn [48], and Tsai and
results in terms of a fuel–oxidizer stoichiometric ratio is not prac- McFadden [49,50], that were incorporated into the NIST HFC mechanism.
tical: as the agent concentration in the oxidizer is increased, u for
Reaction A (cm/mol/s) b Ea (J/mol) References
stoichiometric conditions changes due to the agent’s oxygen de-
mand, as well as due to changes in the equilibrium products as CHF3 + H ) CF3 + H2 3.76  1013 0 54,810 [44]
CO + F + M ) CFO + M 3.09  1019 1.4 2040 [44]
the hydrogen–halogen ratio in the flame changes. Hence, the stoi-
CFO + H ) CO + HF 2.5  1013 0 0 [44]
chiometry effect is presented in terms of the fraction (g) of the CF3 + O ) CF2O + F 1.54  1013 0 0 [45]
available oxidizer (the chamber volume) involved in the reaction CF3 + H ) CF2 + HF 5.33x 1013 0 0 [45]
with the fixed quantity of fuel species from the aerosol can CF2 + O ) CFO + F 2.45  1013 0 0 [46]
CF2 + H ) CF + HF 3.98  1013 0 19,000 [46]
contents.
CF + O2 ) CFO + O 6.62  1012 0 7070 [45]
The fuel quantity is taken to be the contents of the aerosol can CHF3 + O ) CF3 + OH 3.07  1014 0 79,290 [48]
simulator (270 g ethanol, 90 g propane, and 90 g water). The oxi- CHF + H ) CH + HF 0.64  1014 0 0 [50]
dizer consists of ambient air (oxygen, nitrogen, and water vapor) CHF + H ) CF + H2 2.30  1014 0 0 [50]
and the added suppressant. Relative humidity of the test air was
not reported in the FAA tests; however, analysis of local weather
data for the days of the tests indicates that water vapor volume
fractions were always in the range of 0.0016–0.01 (corresponding Table 3
to 7–40% R.H. at 21 °C). Hence, the calculations were performed Additional reactions added to the NIST HFC mechanism to account for C2HF5 reaction
for a water vapor volume fraction Xwv of 0, 0.0125, and 0.025 in with early – forming radicals from propane and ethanol decomposition.

the O2/N2/H2O oxidizer mix, corresponding to 0%, 50%, and 100% Reaction A (cm/mol/s) b Ea (J/mol)
R.H at 21 °C. CHF2  CF3 + C2H5 = CF3  CF2 + C2H6 5.7  1010 0.0 49,400
To summarize: the fuel components and their quantities were CHF2  CF3 + nC3H7 = CF3  CF2 + C3H8 5.7  1010 0.0 43,100
fixed; the ratio of fuel to total oxidizer (N2, O2, H2O, and agent) CHF2  CF3 + iC3H7 = CF3  CF2 + C3H8 5.7  1010 0.0 56,500
was variable, expressed as g, the fraction of chamber volume CHF2  CF3 + C2H4OH = CF3  CF2 + C2H5OH 5.7  1010 0.0 44,400
CHF2  CF3 + CH3CHOH = CF3  CF2 + C2H5OH 5.7  1010 0.0 66,500
(11,400 L) involved in the combustion, and the quantity of each
CHF2  CF3 + CH3CH2O = CF3  CF2 + C2H5OH 5.7  1010 0.0 37,200
oxidizer component in the initial mixture for the calculation was
 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025
A list of potentially important reactions of C2HF5 with the radicals
from initial fuel (propane or ethanol) decomposition was devel-
oped, and the rates were estimated as given in Table 3. The barriers
for the reactions were estimated in Evans-Polanyi fashion by anal-
ogy to that for the reference reaction CHF2  CF3 + CH3 = CF3 –
CF2 + CH4 contained in the NIST HFC mechanism by increasing
the barriers in proportion (0.3) to the decrease in the heat of reac-
tions relative to the reference reaction. The HFC sub-mechanism fi-
nally adopted contained 51 species and 600 reactions. To describe
flame inhibition by CF3Br, the bromine parts of the mechanism of
Babushok et al. [8,51] were adopted, adding 10 species and 74
reactions. That sub-mechanism has been validated in premixed
flame speed and ignition delay studies [8,29,52]. The final mecha-
nism used for the simulations of the aerosol can test fuel, with
C2HF5, and CF3Br, has 177 species and 1494 reactions.
The aerosol can test fuel is predominantly ethanol (about 2/3 of
the energy release), and other models are available that describe
ethanol combustion [53–55] (and even more for propane). None-
theless, we selected the C1–C4 model of Wang as the base-case
(and added the ethanol reactions of Dryer and co-workers) since
extensive validation studies have been performed by the develop-
ers of these mechanisms.
3.4. Perfectly-stirred reactor calculations
Flame extinction caused by suppressants is controlled by the
characteristic times for chemical reaction and transport, as de-
scribed by the Damköhler number Da = sr/sc, in which sr is the flow
residence time, and sc is the chemical time [56]. Hence, an impor-
tant step for understanding flame suppression is to obtain some
measure of the overall reaction rate. Given the explosive, two-
phase, turbulent mixing process occurring during release of the
aerosol can test simulator fuel [3], the reaction zone there may
be simulated reasonably well by a stirred reactor. Further, the stir-
red-reactor blow-out residence time has been correlated with both
the laminar flame speed [57] and with extinction of laminar diffu-
sion flames with added inert suppressants [58], indicating its util-
ity as a measure of overall reaction rate. The residence time in the
reactor s is defined as s ¼ qV=m,_ in which q is the mixture density,
V is the reactor volume, and m _ is the mass flow. Heat losses from
the reactor to the surroundings can also be considered, but are ne-
2500
η ≈ 0.65
50 % r.h.
2000
Reactor Temperature / K
7.7
X C2HF5 = 0 %
1500 14.4
1000
500
0.43 2.4 τ = 32 ms
0 0.0
0.0001 0.001 0.01 0.1
Residence Time / s
Fig. 1. Stirred reactor temperature as a function of residence time for the FAA
aerosol can test fuel, g  0.65, 50% R.H., and C2HF5 added at 0%, 7.7%, and 14.4%
volume fraction in the oxidizer stream.
1019
glected in the present analyses. The governing equations of conser-
vation of mass, species, and energy form a system of coupled non-
linear algebraic equations, which can be solved numerically. In the
present work, we employ the SANDIA PSR code [59].
To obtain the characteristic chemical time at extinction using a
stirred-reactor model, one must determine the blow-out condition.
The process is illustrated in Fig. 1, which shows the reactor tem-
perature as a function of residence time, for three values of the vol-
ume fraction of C2HF5 in the oxidizer. At a very low reactor mass
flow rate, the residence time in the reactor is long, essentially
yielding the equilibrium conditions. As the mass flow in the reactor
is increased, the temperature decreases slightly due to incomplete
reaction, and there eventually becomes a point at which there is
insufficient time to achieve substantial reaction in the vessel;
because of the exponential dependence of reaction rate on temper-
ature, this point is a very abrupt change, where the mixture
‘‘blows-out,’’ without reacting, yielding a blow-out time schem.
Near blow-out, a criterion of <0.5% change in the mass flow rate
was used to determine schem.
Figure 1 shows the blow-out condition for a mixture of the aer-
osol can test fuel, with 65% of the oxidizer in the test chamber
(g = 0.65) at a relative humidity of 50%, for C2HF5 added to the
chamber air at 0%, 7.7%, and 14.4% volume fraction. As indicated,
the characteristic chemical times, schem, obtained for these inhibi-
tor concentrations are 0.43 ms, 2.4 ms, and 32 ms, corresponding
to overall chemical rates in the stirred-reactor (xpsr = 1/schem) of
2330 s1, 416 s1, and 31 s1. As the concentration of added
C2HF5 increases in this range, the characteristic chemical time in-
creases (i.e., the overall characteristic reaction rate decreases).
4. Results
4.1. Equilibrium calculations
The adiabatic flame temperature (of the involved reactants) Tad
was calculated for the FAA aerosol can test in the presence of each
of the three suppressants (C2HF5, C3H2F3Br, CF3Br) premixed in the
chamber air. Calculations were performed over a range of values of
C2HF5
X inh
2000 0
0.072
Tad / K
1500
0.135
1000
0.2 0.4 0.6 0.8 1.0
1 10
η
Fig. 2. Calculated adiabatic equilibrium temperature (Tad) as a function of chamber
volume fraction (g) involved in combustion with the contents of the aerosol can
simulator. Different curves refer to different initial volume fractions of the
suppressant C2HF5 in the chamber air.
1020 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025
g and Xi, as described in more detail in Refs. [28,60], which provide
more details on specification of each of the mole fractions (pro-
pane, ethanol, and water in the fuel mix, and N2, O2, ambient water
vapor and agent in the oxidizer stream) for the initial conditions.
The pressure was 1.01 bar.
The results for C2HF5 are shown in Fig. 2. With no agent, the
shape of the curve mimics the variation in Tad with fuel–air equiv-
alence ratio [61], and the peak adiabatic flame temperature Tad,peak
is reached when about one third of the chamber volume of oxidizer
reacts with the aerosol can contents (g = 0.33). As Xinh increases,
Tad,peak decreases slightly, but still remains near 2200 K, and the
peak value is reached at larger values of g. For inhibitor loadings
greater than Xinh = 0.072, Tad,peak decreases abruptly, and thereafter
decreases more steeply as Xinh increases. This occurs because above
Xi = 0.072, the fluorine content of the system is greater than the
hydrogen content, so HF cannot be formed as the most stable final
product; rather, COF2 is also formed, with the attendant lower total
chemical enthalpy release. The most notable feature of these
flames is that as Xinh increases to the value which suppressed the
aerosol can test explosion, 0.135, the peak Tad is still around
1900 K, and all of the chamber volume (of oxidizer–inhibitor
mix) is required to achieve the peak temperature. Further, at high
values of Xinh, the behavior near the peak Tad is more of a plateau
than a peak, such that a wide range of values of g will produce
nearly the same Tad. This is different from the behavior at low Xinh,
for which Tad drops off on either side of the peak, similar to the
uninhibited case. Since reaction rates are exponential in tempera-
ture, this behavior is likely to affect the overall chemical rates at
low and high Xinh.
The results for C3H2F3Br are shown in Fig. 3. The result is similar
to that of C2HF5; however, the system reaches unity hydrogen to
fluorine ratio at Xi = 0.06, so values above that condition are not
displayed in the figure. As a result, the Tad,peak is maintained nearly
constant at about 2200 K for all values of Xinh up to 0.06. As with
C2HF5, increasing amounts of C3H2F3Br require increasing amount
of chamber volume of oxidizer to achieve Tad,peak, such that with
Xi = 0.06, nearly all of the chamber volume is involved at the
fuel–oxidizer ratio corresponding to Tad,peak. Nonetheless, note that
in the FAA aerosol can test experiment, even with C3H2F3Br added
C3H2F3Br
2000
Tad / K
Xinh
0
1500
0.03
0.06
1000
0.0 0.2 0.4 0.6 0.8 1.0
η Fraction of Chamber Volume Involved in Combustion, η
Fig. 3. Calculated adiabatic equilibrium temperature (Tad) as a function of chamber
volume fraction (g) involved in combustion with the contents of the aerosol can
simulator. Different curves refer to different initial volume fractions of the
suppressant C3H2F3Br in the chamber air.
at Xinh = 6%, the explosion from the aerosol can fire ball was not
suppressed (despite all the oxidizer estimated to be consumed).
As with C2HF5, as Xinh increases with added C3H2F3Br, the curves
for Tad are very flat near the peak—that is, Tad is not very sensitive
to the value of g for high Xinh.
The results for CF3Br are different. As shown in Fig. 4, addition of
CF3Br up to suppression concentration (around 4%) again decreases
the peak Tad only slightly (100 K), but the shape of the curves at
high Xinh are essentially the same as at low Xinh. That is, for peak Tad,
the fraction of chamber volume required is constant (g = 0.33), not
increasing as Xinh increases, as occurs with addition of the other
two agents.
The effects of the inhibitor volume fraction Xinh on the peak adi-
abatic flame temperature are summarized for the three agents
(C2HF5, CF3Br, and C3H2F3Br) in Fig. 5. The left axis shows the peak
Tad, while the right axis shows the value of g required to achieve
the peak Tad (gmax). As indicated, all the agents have a minor (low-
ering) effect on the peak Tad for Xinh < 7%, with CF3Br lowering the
temperature the most. At higher Xinh with the agent C2HF5, the
peak Tad is lower, due to the inability of the system to form HF
(when there are more F atoms in the system than H atoms). The ef-
fect of the different agents on the fraction of chamber volume re-
quired to achieve peak Tad is dramatic. As agent is added, gmax
increases rapidly for C2HF5, and even more rapidly for C3H2F3Br—
but not at all for CF3Br. For the halon alternatives, this is a result
of their fuel-like nature, (i.e., carbon and hydrogen content), so that
the larger molecules have a larger effect on gmax. That is, adding the
agent is like adding fuel to the air stream, so that to oxidize the
aerosol can test fuel, more oxidizer volume is required. As Xinh
goes up, the value of the oxidizer for this purpose is decreased
more, so a higher volume fraction of the chamber is required.
The reason that CF3Br does not show this effect is due to the unique
stoichiometry of this agent in hydrocarbon systems. Since [F]/[H] is
always <1 for CF3Br in the FAA aerosol can test, and since there is
sufficient water in the products, there are always sufficient H and O
molecules left over from the hydrocarbon oxidation (ordinarily in
the form of H2O), to supply the H and O necessary to oxidize
the CF3Br. A global reaction (exothermic) representing this is:
CF3Br + 2H2O ) CO2 + 3HF + HBr (note that HF is a more stable
product for H atoms than H2O).
CF3Br
X inh
0
2000
0.046
Tad / K
1500
1000
0.0 0.2 0.4 0.6 0.8 1.0
Fig. 4. Calculated adiabatic equilibrium temperature (Tad) as a function of chamber
volume fraction involved in combustion with the contents of the aerosol can
simulator. Different curves refer to different initial volume fractions of the
suppressant CF3Br in the chamber air.
 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025 1021

C3H2F3Br

CF3Br

2000 1.0

Tad,max / K

C2HF5
C3H2F3Br

max
0.5

CF3Br

1500 0.0
0 2 4 6 8 10 12 14

Xinh (%)

Fig. 5. Calculated maximum adiabatic equilibrium temperature (left scale) as a function of initial volume fractions of the suppressant in the chamber air, for C2HF5 (4), CF3Br
(h), C3H2F3Br (s). The fraction of chamber volume (g) involved in the combustion which gives the peak temperature is shown on the right scale for each suppressant (same
symbols); error bars: effects of water vapor.

The relative humidity (R.H.) of the ambient air is known to have

a significant effect on the behavior of HFCs in hydrocarbon flames
8
(because of the sensitivity of the system to the fluorine–hydrogen
atomic ratio [62–64]). Hence, the thermodynamic equilibrium cal- C3H2F3Br
culations (as well as the kinetic calculations described below) were
performed for water vapor in the air corresponding to 0%, 50% and
/ bar

100% R.H., at 294 K; i.e., a water vapor volume fraction in the ambi- 6
ent air of 0, 0.0125, and 0.025. For the aerosol can test chamber
max

with no inhibitor, saturating the air with water vapor (100% R.H.)
Pressure Rise at

as opposed to dry air (0% R.H.) lowered Tad by about 6% for stoichi-
ometric and lean conditions (0.34 6 g 6 1.0), while for rich condi-
tions (0.25 6 g 6 0.20), Tad was raised by 1–2%. With addition of
C2HF5, and g > 0.30, Tad was 1–5% higher with saturated air. For
CF3Br addition, Tad was at most 1% lower with saturated air. Note
than in the FAA tests, the variation of ambient water vapor content
was much smaller (6–40% R.H.) than the range examined here,
(0–100%).
Based on flame equilibrium calculations, and using the value of
g which produces the peak adiabatic flame temperature Tad (gmax),
it is possible to estimate the pressure rise in the chamber [28,66].
In the calculation, the value of g is selected, and determines the
fraction of chamber volume oxidizer (O2–N2–agent) allowed to re-
act with the fuel mix in the aerosol can simulator. An equilibrium
calculation (constant P, constant H) gives the volume and temper-
ature of the products, and these are allowed to mix adiabatically
with the fraction of chamber volume (1  g) which is treated as in-
ert. The ideal gas law gives the pressure which this volume of prod-
ucts would have attained. (Note that equilibrium calculations
assuming constant U, and constant V for the reacting fuel and
chamber fraction, essentially the Adiabatic Mixed Explosion Model
[65], gave equivalent results.)
The results of the calculations of pressure rise are shown in
Fig. 6, together with the experimental data from the FAA tests
[1,33]. The error bars (in Figs. 5 and 6) show the effects of water
vapor (the error limits showing the results for 0% R.H., and 100%
R.H.). As indicated, for C2HF5 and C3H2F3Br, the calculations predict
the pressure rise reasonably well, except for the case of
XC2HF5 = 0.135, for which the explosion was suppressed. Similar
4
C2HF5
2
CF3Br
0
0 5 10 15
Xinh (%)
Fig. 6. Calculated pressure rise based on equilibrium thermodynamics evaluated at
gmax, as a function of inhibitor volume fraction in the chamber air, for addition of
C2HF5, C3H2F3Br, or CF3Br (small symbols and lines: calculation with polynomial
curve fits; large circles: FAA experimental data; error bars: effects of water vapor).
to the case of C2HF5 at 13.5%, the pressure rise is not predicted well
with added CF3Br added at around 4%, for which the explosion is
again completely suppressed. Apparently, kinetic effects limit the
extent of reaction with CF3Br, or C2HF5 at the suppression point
(or with CF3Br at lower values of Xinh). Below, we employ stirred-
reactor simulations to estimate the overall rate of reaction of the
aerosol can test fuel with air and suppressant; as in the equilibrium
calculations above, PSR simulations were performed for a range of
values of g and Xinh.
1022 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025

4.2. Perfectly stirred reactor calculations
The initial conditions for the stirred-reactor calculations are
identical to those of the equilibrium calculations, and the results
can be presented in a similar format. The stirred-reactor tempera-
ture Tpsr is evaluated at the reactor residence time just above the
blow-out condition. It is shown as a function of g and Xinh for
C2HF5 and CF3Br in Figs. 7 and 8. For each of these suppressants,
the peak Tpsr is lower than the peak Tad, by 150–400 K, varying with
g, Xinh, and inhibitor type. For C2HF5, Figure 7 shows that as Xinh in-
creases, Tpsr decreases for rich conditions (low g), but increases
then decreases for lean conditions (large g), illustrating the fuel-
like nature of C2HF5 in the stirred reactor. Also, as with the adia-
batic flame temperature, for a given value of Xinh, Tpsr is sensitive
to g for low Xinh, but relatively insensitive to g for high g; i.e., the
curves in Fig. 7 flatten out for high Xinh and g. For CF3Br, Figure 8
shows that for rich flames (g < 0.33), Tpsr is unaffected by addition
of agent, while for lean flames (g > 0.33), Tpsr increases somewhat.
The effect of addition of the agents on the overall chemical rate,
over a range of g and Xinh, is shown in Figs. 9 and 10. For C2HF5, Fig-
ure 9 shows that the effect of C2HF5 on the overall rate depends
upon the value of g. At low g (rich conditions), adding agent re-
duces xpsr drastically. At intermediate values of g (around 0.55),
addition of C2HF5 has no effect on xpsr for Xinh up to about 0.06;
while at high g (lean conditions), adding C2HF5 first increases the
chemical rate, then decreases it. That is, for large fractions of the
chamber air involved, adding suppressant enhances the reactivity
of the system. Conversely, for a given amount of agent, the effect
of g is different at low Xinh versus high Xinh. For example, with no
agent, xpsr is highly dependent upon g, whereas for Xinh = 0.135,
the overall chemical rate is more mildly dependent upon g (i.e.,
the curve in Fig. 9 is relatively flat). Clearly the amount of oxidizer
(air–agent–water vapor) involved in the reaction with the aerosol
can contents has a large effect on the behavior of the system.
C2HF5
10000

X inh
C 2HF5 0

X inh 1000

1700 0
-1
ω psr / s

100
0.072
Tpsr / K

1500 0.072

10

0.133
1300
0.133
1
0.0 0.2 0.4 0.6 0.8 1.0
η
1100
0.0 0.2 0.4 0.6 0.8 1.0 Fig. 9. Overall chemical rate xpsr, for C2HF5 as a function of chamber volume
η fraction (g) involved in combustion with the contents of the aerosol can simulator.
Different curves refer to different initial volume fractions of C2HF5 in the chamber
Fig. 7. Calculated Tpsr as a function of chamber volume fraction (g) involved in air.
combustion with the contents of the aerosol can simulator. Different curves refer to
different initial volume fractions of the suppressant, C2HF5, in the chamber air.

CF3 Br
10000
CF3Br

X inh = 0.046
1000
1700
-1

X inh
ω psr / s
Tpsr / K

100 0
1500

0.024

0.046
10
1300 0

1
1100 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0 η
η
Fig. 10. Overall chemical rate xpsr, for CF3Br as a function of chamber volume
Fig. 8. Calculated Tpsr as a function of chamber volume fraction (g) involved in fraction (g) involved in combustion with the contents of the aerosol can simulator.
combustion with the contents of the aerosol can simulator. Different curves refer to Different curves refer to different initial volume fractions of CF3Br in the chamber
different initial volume fractions of the suppressant, CF3Br, in the chamber air. air.
 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025
Variation in the water vapor content of the air (from Xwv = 0 to
Xwv = 0.0125) has a varying effect on the overall chemical rate in
the PSR. When small amounts C2HF5 are added, the effects are
large. For example, with Xinh = 0.02, added water vapor increases
xpsr by 12% at g = 0.2, and decrease it by 50% at g = 0.94. With
Xinh = 0.06, the effect of water vapor is smaller, decreasing xpsr by
0–13% for the same range of g. With Xinh = 0.14, the decrease in xpsr
with water vapor addition is 26% at g = 0.4, and 8% at g = 1.0. While
these effects are significant, the variations in xpsr in Fig. 9 with g or
Xinh are much larger.
For CF3Br addition, Figure 10 shows that the overall chemical
rate is always reduced, and the effect is much stronger for lean
conditions (large g). This is consistent with the known high tem-
perature sensitivity of the effectiveness of the HBr catalytic radical
recombination cycle [66]. For example, at g = 0.6, CF3Br addition at
Xinh = 0.045 lowers the overall reaction rate by three orders of mag-
nitude (as compared to the uninhibited case), in contrast to C2HF5
(with g = 0.6), for which the inhibitor was relatively ineffective
when added at concentrations up to Xinh = 0.08. For CF3Br, water
vapor has a significant effect on xpsr at g for stoichiometric com-
bustion (0.33), lowering xpsr 12% at Xinh = 0% and 90% at Xinh = 0.05;
whereas at low (0.16) or high (0.64) g, the effect is smaller, about
12–40%.
The results for C2HF5 and CF3Br discussed above are plotted to-
gether in Fig. 11. Curves for no agent, and for C2HF5 and CF3Br at
their suppressing concentration (Xinh,sup = 0.135 and 0.038) and
roughly one half that value ½ Xinh,sup (Xinh = 0.075 and 0.022) are
shown. The importance of the actual value of g in the aerosol can
tests is illustrated by evaluating the effect of agent addition on xpsr
at g = 0.33 and 0.47 (as denoted by the vertical dotted lines in the
figure and listed in Table 4). For the case of g = 0.33, xpsr = 7600 s1
for the uninhibited flame, and 625 s1 and 2700 s1 for CF3Br and
C2HF5 at ½ Xinh,sup, respectively. That is, C2HF5 reduces the reaction
rate more than CF3Br with each added at half its suppression con-
centration. Similarly, when added at Xinh,sup, xpsr = 40 s1 and
980 s1 for CF3Br and C2HF5, so that again, C2HF5 is expected to
slow the reaction rate more. On the other hand, referring to the
dotted line in Fig. 1 for g = 0.47, xpsr = 2900 s1 for uninhibited
flames, and 1100 s1 and 90 s1 for C2HF5 and CF3Br at ½ Xinh, ext,
and 55 s1 and 14 s1 at Xinh,sup, and so that for g = 0.47, the inhibi-
tion by CF3Br is stronger. At higher values of g, the superior inhibi-
tion by CF3Br is even greater.
It is clear from the above discussion that the actual fraction of
the chamber gases involved in the reaction with the aerosol can
10000 X inh = 0 %
X CF3Br = 2.4 %
1000
X CF3Br = 4.6 % X C2HF5 = 7.2 %
-1
ω psr / s
100
X C2HF5 = 13.3 %
10
1
0.0 0.2 0.4 0.6 0.8 1.0
η Fraction of suppression volume fraction (%)
Fig. 11. Overall chemical rate xpsr, for C2HF5 and CF3Br as function of g; curves are
given for each agent at the extinction volume fraction, and approximately one half
of that value.
1023
contents has a large effect on the expected suppression efficiency
of the two agents. As discussed above, for the agent C2HF5 it is pos-
sible to estimate the values of g from the pressure rise observed in
the experiments (and shown in Fig. 6). That is, if fairly large values
of g are not employed, it is impossible to have enough energy re-
lease to get the pressure rise observed in the FAA tests. Using Fig-
ure 5, we obtain the value of gmax (i.e., g necessary to give Tad,
which was required to yield the observed pressure rise for C2HF5
and C3H2F3Br). These values of g are shown as the solid circles in
Fig. 11. As shown, for C2HF5 at Xinh = 0.075, g must be about 0.47
to get the observed pressure rise, while for Xinh = 0.135, g  1.05
is required. As indicated, at the higher values of Xinh, values of g
close to unity are required to give the observed pressure rise. For
CF3Br, the specification of g is more difficult, since, as discussed
above, the predicted pressure rise with CF3Br is insensitive to the
value of g used in the calculation, so the pressure rise cannot be
used to estimate g. (Of course, the actual pressure rise for CF3Br
is even less than that predicted based on thermodynamics, due
to kinetic influences.) If the actual g in the FAA tests were 0.33
for CF3Br, then the PSR calculations suggest that it should not
extinguish the aerosol can test as effectively as C2HF5 (which is
contrary to the experimental result). Hence, it is more likely that
the actual g for the aerosol can test with CF3Br addition is higher
than 0.33. If g were about 0.47 for either agent, then the explana-
tion shown by Fig. 11 is consistent with the FAA experimental re-
sults for the agents, since CF3Br is more effective than C2HF5 at
g = 0.47, as shown in Table 4. The sensitivity of the inhibitor effec-
tiveness to the value of g is consistent with the findings in some of
the FAA tests [67] that a delay in the energy application to the igni-
ter had a large effect on the explosion properties of the system.
That is, delaying the spark increases the mixing time prior to igni-
tion, changing the effective value of g in the system (as well as
changing the local gas composition near the ignitor). Similarly,
tests with CF3Br with added N2 in the oxidizer stream found the
combination to work better than either agent alone. This is also
likely due to the enhanced effectiveness of CF3Br at lower temper-
ature, as illustrated in the simulations above for which higher g
leads to lower overall reaction rate (i.e., higher dilution with the
relatively inert air stream lowers the peak temperature, increasing
the effectiveness of the HBr catalytic cycle).
To highlight the importance of the value of g on the effective-
ness of the agents in reducing xpsr, Figure 12 shows, xpsr, as a func-
tion of the fraction of the suppressing concentration. The different
curves in the figure are for different assumed values of g (0.33,
0.47, and gmax). The following conclusions can be drawn from the
figure:
1. More agent generally reduces xpsr, for the assumed values of g.
2. For the case g = 0.47, there is little change in xpsr for the curve
for C2HF5 up to 30% of the suppression value.
3. For C2HF5 (blue curves), the reduction in xpsr with addition of
agent is similar regardless of the value of g; i.e., for g = 0.33,
g = 0.47, or g(Tad,peak).
Table 4
Overall chemical rate predicted by the stirred reactor calculation for C2HF5, CF3Br, and
2-BTP simulant at values of constant g = 0.33 and g = 0.47.
Overall chemical rate, xpsr (s1)
g: 0.33 0.47
Agent: C2HF5 CF3Br C2HF5 CF3Br
0 7600 7600 2900 2900
50 625 2700 1100 55
100 40 980 90 14
1024 G.T. Linteris et al. / Combustion and Flame 159 (2012) 1016–1025
10000
CF3 Br, η = 0.33
1000
ω psr / s -1
100 C2HF5, η= 0.47
C2HF5, η= 0.33
C2HF5, η=ηmax
CF3 Br, η = 0.47
10
0 50 100
Xinh / Xinh,supp (%)
Fig. 12. Overall chemical rate xpsr, for all C2HF5 (D) and CF3Br (C) as function of the
fraction of suppression concentration, for different values of g.
4. The effectiveness of CF3Br is very sensitive to the value of g.
5. For CF3Br to be more effective than C2HF5, g must be greater
than about 0.4.
5. Conclusions
Chemical equilibrium and perfectly-stirred reactor calculations
have been performed for the purpose of understanding the unex-
pected enhanced combustion in the FAA Aerosol Can Explosion
simulation test. The equilibrium calculations were used to predict
the overpressure in the FAA tests with C2HF5 or C3H2F3Br added at
sub-inertion concentrations. With either of these agents, the ob-
served pressure rise is a strong function of both the fraction of
chamber volume involved in the combustion (g), and the amount
of added agent. At increasing agent volume fractions, the observed
large pressure rise is predicted only if a large fraction of the cham-
ber is involved, corresponding to near stoichiometric conditions
(including oxygen demand from reaction of the agent), with reac-
tion to equilibrium products. On the contrary, the pressure rise
with added CF3Br is shown to be nearly independent of both the
fraction of chamber volume involved, and the amount of added
CF3Br. This result is shown to be due to the atom balance in the
CF3Br–hydrocarbon–air system, for which added CF3Br is predicted
to never show an enhanced pressure rise (even if the typical strong
chemical inhibition with CF3Br were not to occur). Nevertheless,
the high reactivity for the C2HF5 and C3H2F3Br at the concentra-
tions of the FAA tests are somewhat unexpected.
To understand the role of kinetics, the inhibition effects of the
agents on the overall reaction rate of the system were examined
through stirred reactor calculations. Calculations were performed
for C2HF5, and CF3Br, over a range of agent concentrations and frac-
tion of chamber oxidizer involved in the combustion. The amount
of oxidizer (air + agent) in the test chamber which participates in
the high-temperature reaction with the fuel (i.e., the amount of
chamber test volume which mixes with and reacts with the fire
ball of the fuel reaction), is found to have a major influence on
the relative effectiveness of each agent.
For the premixed system modeled by the PSR, the role of excess
oxidizer (air plus agent) entrainment with the reaction zone varies
with the agent. For C2HF5, the reduction in the overall reaction rate
with addition of agent is found to be relatively insensitive to the
fraction of chamber volume involved (g). On the other hand, for
CF3Br, the reduction in the overall reaction rate with addition of
CF3Br is highly dependent upon g. Hence, the relative effectiveness
of these agents for reducing the overall reaction rate in the stirred
reactor simulations is highly dependent upon the premixed state of
the reactants—the assumed composition of which depends upon
the mixing state in the FAA test. That is, the relative effectiveness
of these agents for inerting the explosion of the FAA test may be
dependent upon the particular test conditions employed.
Acknowledgments
The authors thank Wing Tsang of NIST, and John Reinhardt at
the FAA Technical Center for essential input to the work. Ken Smith
and Med Colket at the United Technologies Research Center per-
formed ab initio calculations for C3H2F3Br and graciously provided
the thermodynamic data for the C3H2F3Br molecule, allowing us to
perform the thermodynamic calculations. Mike Zehe at NASA
Glenn Research Center assisted with implementing the C3H2F3Br
data in to the NASA CEA program. Brad Williams at NRL kindly pro-
vided his changes to the NIST HFC mechanism. The work was sup-
ported by The Boeing Company.
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