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CITATIONS
5 AUTHORS, INCLUDING:
James G. Quintiere
Richard E. Lyon
SEE PROFILE
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F. J. Diez
Rutgers, The State University of New Jersey
56 PUBLICATIONS 132 CITATIONS
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a r t i c l e
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Article history:
Received 30 May 2012
Received in revised form 25 October 2012
Accepted 12 February 2013
Available online 28 March 2013
Keywords:
Combustion of polymers
PMMA
Low pressure
Burning rate
Time to ignition
Flammability
a b s t r a c t
An experimental study of the ammability properties of PMMA at low pressures and oxygen concentrations was performed. The work was motivated by the importance of these effects on re safety in the aviation industry. Measurements were obtained in a mass loss calorimeter inside a large 10 m3 pressure
vessel capable of reaching pressures as low as 0.1 atm. The PMMA ammability was characterized by
measuring the burning rate and the time to ignition of small test samples. These were ignited and burned
under different external heat uxes, total pressures and oxygen concentrations. The combined effects of
pressure and oxygen concentration on the burning rate, combustion ow eld, and ignition were evaluated. Results showed that at low pressure, the burning rate was less intense with a decrease in the mass
loss rate. However, the reduction in pressure caused a shortened ignition delay time. Experimental measurements were compared with a simple analytical model showing good agreement. The results also
show how pressure and oxygen concentration contributed to the heat transfer from the ame. The model
revealed that a single function in oxygen and pressure could account for both ame radiative and convective effects. As a result, a power law t was obtained for the relation of the combined pressure and oxygen
effect on the burning rate. This correlation shows a good agreement with the measurements and predicts
the burning rate behavior for the full range of pressure and oxygen tests.
2013 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
1. Introduction
Pressure and buoyancy effects on the ammability and burning
characteristics of solid materials have been previously extensively
explored in low gravity and micro-gravity environments. These results have been directly applied to re prevention and re-ghting
strategies on spacecraft systems [1,2]. However, res can also occur in low pressure environments associated with high altitude
locations and inside sub-ambient pressurized compartments.
Burning characteristics and rates at high altitude locations (local
pressure is up to 35% less than sea level) and the pressurized cabin
of a cruising aircraft (at 10 km altitude the local ambient pressure
is 0.26 atm) play an important role in characterizing the ammability of solid materials. Similarly, the role of local oxygen concentration is extremely important to the burning of solid materials
due to their strong dependence on oxygen concentration at the
ame zone [3]. Since the burning of these solids occurs in a diffusion ame mode, oxygen transport is often one of the major factors
inuencing ignition criterion and the sustainment of combustion
[4,5]. Therefore, pressure and local oxygen concentration are both
expected to signicantly inuence the ammability of solid
Corresponding author.
E-mail address: diez@jove.rutgers.edu (F.J. Diez).
0010-2180/$ - see front matter 2013 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.combustame.2013.02.019
1520
Nomenclature
A
Cp
CHF
D
Gr
hc
k
l
lm,e
L
Lf
LFL
_ 00ig
m
Nu
p
q_ 00e
q_ 00ext
q_ 00f ;c
q_ 00f ;r
q_ 00py
q_ 00rr
r
s
Tf
Tf,crit
tig
Tv
T1
TRP
V
Xr
Y O2 ;1
ame temperature
adiabatic ame temperature at LFL
ignition time delay
material surface vaporization temperature
ambient temperature
thermal response parameter
volume of the gas
ame radiative fraction
ambient oxygen mass fraction
Greek symbols
Dhc
heat of combustion
Dhpy
energy per unit mass loss to vaporize the solid
ef
ame emissivity
jf
absorption emission coefcient
l
viscosity
q
density material burnt
r
StefanBoltzmann constant
s
transmissivity of the ame between the heater and the
material
1521
Fig. 1. (a) Front and (b) side view of the calorimeter and enclosure (used to control the amount of oxygen). Air is fed in through the bottom of the enclosure and exhausted out
through the top.
To closely control the amount of oxygen available to the polymer sampling during the burning, all the measurements are performed inside a smaller container placed inside the pressure
vessel. This container shown in Fig. 1 is 76.2 cm tall with a crosssectional area 62.5 62.5 cm2. Through the use of the externally
applied constant air ow, the oxygen concentration can be varied
locally inside the container, without the need to ll the entire pressure vessel. The airow enters through the bottom of the container
via a 12.7 mm diameter pipe perforated every 1 cm to create a uniform updraft. The air exits the container through the top via a
7.62 cm exhaust port pipe, expelling the exhaust gas into the inside
of the pressure vessel. To avoid exhaust gas air recycling, a very
small positive pressure difference exists between the smaller
chamber and the pressure vessel during the tests to shield the test
environment from the conditions in the larger pressure vessel. The
supplied air, after it has passed through the smaller container, is
then removed via a vacuum pump to the outside. The air entering
the internal container is maintained at a specied oxygen concentration, Y O2 1 , that ranged from 12% to 21% depending on the particular tests as shown in Table 1. The required oxygen concentration
for each test is obtained by mixing the house air with nitrogen to
produce the required gas mixture. The system is capable of reliably
producing and maintaining oxygen concentrations in nitrogen
from 21% to 10% by volume. The diluent nitrogen was produced
Table 1
List of test conditions.
Test conditions
Pressure (atm)
Oxygen concentration (%)
External heat ux (kW/m2)
Inlet air temperature (C)
Air ow rate through pressure vessel (l/s)
Polymer sample thickness (mm)
Values
1522
3. Experimental results
Video recordings provided direct observation of the ame shape
and color during the PMMA ammability study. Some typical
images of burning PMMA samples are shown in Fig. 2 where no
external heat ux was applied and the oxidizer mole fraction
was maintained at 21% for the various atmospheric pressure conditions. The images show substantial differences in ame height,
ame color, and ame shape as a function of external pressure.
In terms of luminescence from the ame, the ame color changed
from a bright yellow at standard pressure to a dim blue color at
low pressures with an associated reduction in the ame luminosity. This change in ame color and overall luminous intensity is related to both the amount of soot generated from the PMMA
Fig. 2. Typical images of burning PMMA samples for 21% O2 with no external heat ux applied showing ames at (a) 1 atm, (b) 0.68 atm, (c) 0.47 atm and (d) 0.18 atm. The
images show substantial differences in ame height, ame color, and ame shape as a function of external pressure. (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)
Fig. 3. Typical images of burning PMMA samples for 21% O2 and a large external heat ux applied of 50 kW/m2 showing ames at (a) 0.48 atm and (b) 0.18 atm.
Fig. 4. Typical measured mass loss rate as a function of time from the PMMA
burning sample for 0.68 atm and 21% O2 at 16 kW/m2 external heat ux. Results are
smoothed using a linear 21 point SavitzkyGolay lter to reduced measurement
and readout noise. Steady state is observed between t 400 s and t 700 s.
1523
Fig. 5. Ignition times normalized and plotted versus the external heat ux for 1 atm
and 21% O2. The experimental results are tted by the theoretical model in Eq. (4)
(CHF = 8.2 kW/m2).
results showed that for the PMMA sample thicknesses used, steady
burning could not be achieved, due to the very high mass loss rates
and limited sample sizes. Thus, for the larger external heat uxes,
thicker PMMA samples were used to ensure that steady burning
was achieved during the test time.
Using the mass loss rate curves for various environments, several key combustion parameters can be extracted. The time to ignition (or ignition delay time) is a relevant parameter for
determining the ammability of the sample. This parameter can
be considered a sum of three distinct steps that help contribute
to the delay of ignition. Initially the solid has to be heated to a high
enough temperature to cause the evolution of pyrolysis gases to be
given off. The second step involves the transport of the fuel
through the boundary layer and the mixing of the fuel with the oxidizer. The last step involves the time it takes for the mixture to sustain propagation from the electric arc pilot. Since the main
objectives of the study are to determine the effect of low-pressure
environments and normal to low oxygen concentrations, ignition
times were determined from the greatest change in mass loss rate
correlated with the observance of ame by recorded video data.
Once the individual ignition times were achieved, they were normalized and collapsed by plotting them versus the external heat
ux as shown in Fig. 5 for ambient pressure conditions. The time
1=2
to ignition should scale as tig with increasing external heat ux
[25]. This decrease in ignition delay time is expected as an increase
in external heat ux enhanced the mass transfer at the PMMA surface, leading to quicker production of ammable mixtures at the
ignition location.
Time to ignition values were obtained experimentally for all the
test conditions in Table 1 (range of pressures, external heat uxes,
and oxygen concentrations). These results are shown as a function
of pressure in Fig. 6 for the ve external heat ux conditions imposed in this study. Each test condition was repeated six times to
reduce the experimental uncertainty with both the average value
and the standard deviation shown in Fig. 6. The results show a
weak dependence of time to ignition with pressure at the lower
range of the externally applied heat ux conditions. This weak
dependence then disappears as the heat ux is further increased,
and the time to ignition is essentially independent of pressure
above an external heat ux of 16 kW/m2. Due to the nonlinear effect of the external heat ux on the ignition delay time, the error
bars on the higher heat ux conditions are much wider, while
the repeated lower heat ux tests showed a much smaller variation
in ignition times. These experiments suggest that the effect of pressure on time to ignition is negligible at sufciently high heat uxes
and hence can be neglected.
1524
Fig. 9. Measured steady burning mass ux as a function of oxygen mass fraction for
different pressures at a constant heat ux of 16 KW/m2. Results are compared to the
analytical model in Eq. (13) to help explain the measurements.
1525
4. Analytical model
The theoretical analysis will address ignition and burning rate
as a function of external heat ux atmospheric pressure, and oxygen. The model specically addresses the burning in the cone calorimeter conguration, or one comparable in orientation and
sample size. However, the model can be extended to larger pool
re orientations. The framework of the modeling follows established theoretical based correlation techniques using property
parameters that are derived from data taken at several heat uxes.
We will use such data from normal atmospheric conditions of pressure (14.7 psi) and oxygen (21%) to derive results at other pressure
and oxygen conditions. The modeling approach is supported by
studies from Tewarson et al. [3,5,20,23] and Hamins et al. [24] on
predicting the burning rate of pool res. The basis of the approach
for ignition and burning rate is described in more detail in Quintiere [25]. Here, only steady burning will be considered, and kinetic
effects in the solid phase are not addressed.
4.1. Ignition
4.1.1. Ignition delay time
Ignition modeling follows the approach used in ASTM E-1321
with some modication. This is described in detail in Quintiere
[25, p. 176187]. It has been found that piloted ignition data for
real materials follows the following behavior, except near the critical heat ux (CHF). The ignition time delay can be related to the
applied external heat ux, q_ 00ext , as shown in the following equation.
tig
2
TRP
q_ 00ext
TRP
p
4
12
kqcp T ig T 1 ;
This result can be derived from the heat conduction in a semiinnite solid with linearized surface heat loss in the limit of small
time or high external heat ux [25].
Fig. 10. Measured mass ux at ignition as a function of pressure for 21% O2 and compared to the pressure-dependent sample ashpoint and repoint for (a) 10 W/m2 external
heat ux and for (b) 12 W/m2 external heat ux.
1526
This equation does not accurately represent experimental ignition data when the external radiant heat ux approaches the CHF.
The CHF can be estimated by computation through an energy balance at the surface of the material just before ignition to a sustained ame at very long time. At very long time, the external
heat ux will be the CHF with the material effectively at a uniform
temperature equal to its ignition temperature. There is no heat loss
by conduction into the material. Consequently the external heat
ux is equal to the radiative and convective surface losses and
the energy required to pyrolyze the material to achieve its lower
ammability limit concentration (LFL) at the pilot location. Here,
no inclusion of surface oxidation is taken, as we assume it will
be small for our application. However, at higher than ambient oxygen concentrations, it should be considered as a source of energy to
the surface. Under the conditions specied the CHF can be found by
CHF
CHF p
t
1
exp
ig
q_ 00ext
TRP
R T f ;crit
LFL
T1
cp dT cp T f ;crit T 1
Dhc
Dhc
_ 00ig
m
hc
LFL
cp
Drysdale [27, p 88] indicates that the LFL is fairly constant below normal atmospheric pressure down to about 0.1 atm
(1.5 psi). He also shows that the LFL is fairly constant for
oxygen concentrations above that of a normal atmosphere
conditions. At lower fuel concentrations, piloted ignition will not
be possible. The lower limit can be estimated using the fact that
_ 00ig
m
hc 1530 K
Dhc
_ 00ig Dhpy
q_ 00py m
4.1.2. Critical mass ux for ignition
A theoretical analysis of the critical mass ux at ignition (ashpoint) and at extinction (re point) has previously been put forth
by Lyon and Quintiere [26] showing good agreement with polymer
data. The mass ux at ignition can be related to the LFL (as a mass
fraction concentration) using convective mass transfer theory with
equal Prandtl and Schmidt numbers applicable to air:
where Dhpy is the energy per unit mass loss to vaporize the solid.
4.1.4. Effect of pressure and oxygen
To bring closure to the analysis in predicting the time to ignite,
Eq. (4) can be used to correlate ignition delay times over a wide set
of conditions. However, there are several restrictions to its use that
should be noted. Eq. (4) will not hold below a pressure of approximately 0.1 atm due to kinetic rates that will signicantly slow at
low pressures, increasing the time to ignite or rendering the material nonammable. At oxygen concentrations below about 12%
(vol.) no ignition is likely. Additionally, two crucial parameters that
will affect the time to ignite are the heat of combustion and the
convective heat transfer coefcient. From Eq. (7), as long as the
LFL does not vary signicantly (above 0.1 atm and above 12% oxygen) the heat of combustion should be invariant. However, the heat
transfer coefcient will vary with pressure.
1527
Nu Gr 1=4
1=4
2
q
hc l
DT 3
g
l
k
l
T
10
hc q1=2 p1=2
This suggests a pressure dependence on the heat transfer coefcient without combustion.
Hence, for the same temperature conditions at ignition (or aming), the same size material, and with density proportional to pressure by perfect gas theory, it follow that the heat transfer
coefcient is proportional to pressure to the one-half power. If conditions were turbulent, the pressure scaling would shift to the twothirds power, and in forced ow this would vary as one-half power
for laminar conditions and one-third power for turbulent conditions. In the present application, the one-half power for free and
forced conditions per Liu et al. [28] is used to represent the dependence of the convective heat transfer coefcient with pressure:
hc 0:012
1=2
ppsi
0:00313ppsi1=2 kW=m2 K
14:7
11
kW=m
12
_ 00 L
m
hc
k
Y o2 ;1 Dhc =r1 X r cp T v T 1
cp ek 1
q_ 00f ;r sq_ 00ext rT 4v T 41
13
s ejf lm;e
14
lm 3:6V=A
15
pD=23
0:6D 0:677 s
lm;e 3:6
2pD=22
2
3
16
lm;f
p D2 L
4
0:9
pDLf 2 p4 D2
Lf =D
1:01s
Lf =D 1=2
Lf =D
D
Lf =D 1=2
17
Here Lf cannot exceed the vertical duct height of the cone calorimeter, as that would limit the vertical ame height.
The incident ame heat ux is given as
q_ 00f ;r ef rT 4f T 41
18
ef 1 ejf lm;f
19
1528
15:6 q
or
Lf
D
2=5
Y o2 ;1 cp T 1 3=5
Q_
p 5=2
Dhc =r
gD
1 T 1 cp
0:23Q_ 2=5
14:7
p
2=5
0:233
Y o2 ;1
3=5
20
1:02
2
p
po
21
22
T f T 1 65001 X r Y ox;1 K
The ame radiative fraction likely is affected by pressure and
oxygen, especially as the ame nears extinction due to changes
in the soot volume fraction. It is well known that for res over
1 m in diameter, the radiation fraction also drops due to soot
blockage. The latter does not apply to the present application,
and the former cannot be described due to lack of detailed experimental data about the soot levels as a function of the conditions
varied in this study. So in the current application, the radiation
fraction will be taken as a constant for a given fuel.
4.2.4. Empirical analysis
As an approximation to Eq. (13), the ame energy balance can
be written as
23
q_ 00f ;c / p1=2 Y o2 ;1
24
q_ 00f ;r / p2 Y 4o2 ;1
This means that
26
This functionality is investigated for the data as a way to simplify the inuence of pressure and oxygen on the burning rate, at
least where the above approximations are valid.
1:02
jf jo
_ 00 L q_ 00ext rT 4v T 41 functionp1=2 Y o2 ;1
m
25
_ 00
m
q_ 00ext q_ 00rr
64p1=2 Y O2 ;1 1:3
L
27
where q_ 00rr rT 4v T 41 is the re-radiation heat ux from the surface. This is a simple relation that works for the measurements of
all PMMA samples burned at different pressures, oxygen concentrations and external heat uxes. By plotting the y-axis in Eq. (27) as
_ 00 q_ 00ext q_ 00rr =L it allow us to show that the data is independent
m
of heat ux. The only exceptions are the results for external heat
uxes above 50 kW/m2 that are not shown since this large external
heat ux dominates the mass loss rate.
The above simple scaling does not include modeling of a nite
chemical reaction timescale, which can play an important role in
ignition and extinction. A Damkohler number could be created
which combines the chemical reaction timescale with that from
the convective heat transfer. At the highest heat ux cases examined in this study, it is possible that the timescale associated with
convective heat transfer combined with the very strong buoyancy
generated in the ame oweld has decreased to be of the same
order as the fundamental chemical timescale [38]. This introduction of a Damkohler number dependence would allow for the
extension of the proposed model to higher heat ux values. At
1529
these higher externally applied heat ux values, the ame temperature may also be signicantly affected, inuencing the diffusion
coefcient and introducing a Lewis number effect [39]. These higher order effects may limit the correlation of this model with very
high external heat ux cases (as seen and discussed in Fig. 6).
Due to these signicant added complexities, we have chosen to
limit the applicability of our model to a lower externally applied
heat ux range where these additional scaling parameters are of
less import.
6. Conclusion
An experimental study of the ammability properties of PMMA
at low pressures and oxygen concentrations was performed in a
large 10 m3 pressure vessel, capable of reaching pressures as low
as 0.1 atm. The PMMA ammability was characterized by the burning rate and time to ignition of 10 10 cm2 samples. Tests were
performed at different applied external heat uxes ranging from
10 to 72 kW/m2 with burning rates obtained during steady burning
for all cases. Other test conditions included oxygen concentrations
from 1221%, and pressures from 0.18 to 1 atm. For each burn test
condition, the experiment was repeated 6 times in the mass loss
calorimeter inside the pressure vessel.
Experimental measurements allowed the observation of the effect of pressure and oxygen concentration on the burning rate. The
results show that at low pressure the burning was less intense,
which is shown by the decrease in the mass loss rate. On the other
hand, the reduction of pressure causes the sample to ignite faster
and at a lower critical mass ux, but this is only relevant at low levels of external heat ux. In general, the experimental measurements showed a good agreement with the power law t
obtained for the relation of the combined pressure and oxygen effect on the burning rate. This correlation predicts the burning rate
behavior for the full range of pressure and oxygen measurements
obtained.
Experimental measurements were compared with a simple analytical model. The results show how pressure and oxygen concentration contributed to the heat transfer from the ame. Pressure
affects the heat transfer trough the convective heat transfer coefcient and the effective soot emitter parameter. The convective heat
transfer coefcient affects the convective heat losses which are
diminished at low pressure, causing the sample to ignite faster.
Similarly it explains the decrease in the burning rate through lowering of the heat feedback mechanism to the sample surface as
well as the decrease in the critical mass ux at ignition through
the reduction in the available oxygen. The lower oxygen content
the reduces then ame temperature, thereby lowering the net heat
ux back to the sample surface.
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