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Autoignition of combustible fluids in porous insulation

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Article  in  Combustion and Flame · December 1994

DOI: 10.1016/0010-2180(94)90047-7

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COMBUSTION AND FLAME 99:541-550 (1994) 541

Autoignition of Combustible Fluids in Porous

Insulation Materials
A. C. MclNTOSH,* M. BAINS, W. CROCOMBE, and J. F. GRIFFITHS
Departments of Fuel and Energy (A.C.M.) and Physical Chemistry (M.B.; W.C., J.F.G.), Leeds University,
Leeds, LS2 9JT, UK

The leakage of combustible fluids into the lagging of pipework in the process engineering industry can be
very hazardous because of the increased residence time for oxidation as the liquid resides in the porous
medium and also the substantially modified heat and mass transfer rates when compared with ignition at hot
surfaces. The exothermic reaction can lead to ignition or at least severe self-heating with the consequent
damage of pipework, etc. Experiments have been performed to simulate this hazard. The thermal behavior of
a number of combustible liquids placed in porous material has been monitored and evidence is presented in
this work that self-heating can indeed take place. It has been found that autoignition occurs at an important
"'watershed" oven temperature that is related to the volatility of the combustible fluid. A mathematical
model for the autoignition of combustible liquid in an inert porous material is presented. The simple model
takes a spatially uniform approach to both the energy equation and the liquid equation for the fluid and
predicts a watershed temperature such that for a given concentration of fluid in the porous material, the
thermal behavior of the system alters abruptly. For all practical purposes, thermal runaway is predicted
beyond this watershed condition even though the classical Semenov theory simply predicts an eventual decay
to a stable steady state, with no strict "criticality" prediction. The watershed temperature is shown to depend
on volatility and reactivity.

INTRODUCTION is also a common problem of lagging fires in

Current Understanding of Ignition
in Insulation Materials
This paper is concerned with the fundamental
understanding of a recognized industrial haz-
ard which may occur when a combustible liq-
uid leaks from a hot pipe into porous insula-
tion material [1]. The fluid becomes dispersed
over an extremely high internal surface area
and ignition may result from the exothermic
oxidation of the fluid in contact with the air
within the hot, porous structure. The purpose
of this work is to interpret this behaviour in a
way which does not rely so much on the em-
piricism that the subject has so far received.
The consequences of spontaneous fires in
insulation materials are, at best, costly if they
lead to temporary shutdown of chemical plant
and, at worst, disastrous if the temperatures
attained cause the rupture of pipework. There
* Corresponding author.
Presented at the Twenty-Fifth Symposium (International)
on Combustion, Irvine, California, 31 July-5 August 1994.
Copyright © 1994 by The Combustion Institute
Published by Elsevier Science Inc.
ships, as a result of the spillage of Diesel fuel
over hot insulation materials. Considerable
practical data on the performance of a number
of classes of fluids dispersed within a variety of
insulation materials have been published [2],
but this work falls far short of attacking the
fundamental understanding and interpretation
of the hazard or offering a rigorous framework
from which potential hazards may be pre-
dicted. Despite its extensive nature, that study
was directed only at a test of the validity of an
empirical rule [3], which has been invoked to
assess the potential fire hazard from insulation
in terms of the Autoignition Temperature
(AIT) and Flash Point (FP) of the combustible
liquid. These parameters are determined by
specific tests as laid down by American, British,
and European standards (ASTM, BS, and CEC
respectively). The form of the relationship is
AIT
> 1.55 (all temperatures in °C),
(AIT - FP)
which suggests that ignition may be possible
when a liquid undergoes an exothermic reac-
0010-2180/94/$7.00
542
tion at temperatures at which its volatility re-
mains relatively low (since flash point is higher
for lower volatility and thus (AIT-FP) is
smaller).
In the present paper we demonstrate experi-
mentally the phenomenon of autoignition of
combustible fluids in porous insulation materi-
als and establish a simple theoretical model for
the onset of thermal runaway, including a mod-
ified definition of ignition. This theoretical
model is then used to explore the relationship
between volatility and reactivity. In this work,
we are not attempting to model the later stage
of high-temperature (smoldering) propagation.
Normally the exothermic processes that take
place in porous media (such as carbonaceous
or cellulosic materials) are caused by oxidation
at the extensive internal surface by oxygen in
air diffusing into the structure. However, it is
known that in the early stages of development,
and up to the point that might be termed
"ignition," there is generally sufficient oxygen
available within the pore structure for its sup-
ply by diffusion not be be a rate-controlling
step. A number of earlier papers discuss this
matter [4-7]. In fact, the rate is controlled by
the amount of combustible liquid present since
the loss of volatile combustible fluid due to
evaporation is significant. This is particularly
true when there is little combustible fluid left,
since at this point the balance between evapo-
ration and ignition is crucially affected by the
amount of fluid present. Nevertheless, when
ignition has developed, the rate of propagation
of the combustion becomes controlled by the
rate of oxygen diffusion. The exothermic reac-
tions of this later stage (which is usually termed
smoldering combustion) involve volatiles from
the degradation or partial oxidation of the
original primary material.
Experimental Background and Choice
of Combustible Fluids
It is not easy to classify "reactivity" of materi-
als that may be involved in fires within insula-
tion materials in an absolute way since, ulti-
mately, the problem concerns relative rates of
heat generation and loss, along with mass loss
by evaporation. Thus in order to establish a
relationship between "autoignition tempera-
A . C . MCINTOSH ET AL.
ture" and volatility, a series of identical au-
toignition tests in a uniformly heated oven
were performed on a standardized block of
insulation material impregnated with pure liq-
uids of very similar reactivity but of increasing
volatility. Our intention was to make the exper-
iments easier to conduct by using an analogous
series of compounds with lower volatility than
that of liquid alkanes, but with similar reactiv-
ity. A related class of compounds is the series
of alcohols from 1-CfH13OH to 1-C11H23OH
(B.Pt. 425-500 K). These are obtained in pure
form more more readily than the C15-C22 n
alkanes (B.Pt. 425-475 K) and although not
yet subjected to independent experimental test,
it may be presumed that the length of the
carbon chain is such that the variation from C 6
to C11 is unlikely to significantly affect the
reactivity. The principal aim was tO conduct
experiments on the thermal runaway of com-
bustible fluids which distinguished the conse-
quences of different volatility under conditions
of similar chemical reactivity.
Background to the Mathematical Model
In the theoretical investigations of this phe-
nomenon, a mathematical model is developed
in a very simplified form. The exothermic oxi-
dation is represented as a single step reaction
obeying an Arrhenius temperature depen-
dence. Spatial uniformity of temperature and
dispersion of reactant within the block are
assumed, so that the mass and energy conser-
vation equations may be treated as first-order
differential equations. Such an approach is ac-
ceptable in the initial stages of self-heating of
the combustible liquid, prior to the onset of
smoldering combustion. As in the Semenov
theory of thermal ignition, the energy conser-
vation equation has a heat release term associ-
ated with the exothermic oxidation (but which
is now dependent on the combustible fluid
concentration) and also two heat loss terms.
The first is controlled by a surface heat trans-
fer coefficient (as in the classical Semenov
analysis), but the second is associated with the
evaporation of the fluid from the porous
medium. Coupled with the energy equation is a
combustible fluid conservation equation de-
scribing the oxidation process and (slow) evap-
AUTOIGNITION OF FLUIDS IN INSULATION MATERIALS
oration of the fluid. There will also be a con-
servation equation for the combustible vapor
which is decoupled in this simplified model.
The evaporative term controls the reduction of
the combustible fluid concentration and
thereby affects the chemical reactivity as time
progresses.
In reality there are other important effects,
such as diffusion of heat and reactant vapor
within the porous material, the porosity of the
insulation itself, and even mass transport of
the flammable fluid both out of and into the
material in certain circumstances. Neverthe-
less, even from this simple approach which
strips the problem down to the essential physics
of the phenomenon, there is revealed a surpris-
ingly rich pattern of behavior due to the com-
petition between the evaporation of the com-
bustible liquid and its reaction with the air.
EXPERIMENTAL PROCEDURE AND
RESULTS
Apparatus and Procedures
The minimum ignition temperature of the fluid
in the insulation material (5 cm cube, density
350 kg m -3) was established by mounting a
series of experiments in which the block, freshly
impregnated with one of the alcohols in the
C6-C1~ range, was located in a recirculating
air oven thermostatted at successively in-
creased temperatures for each experiment. An
oven temperature was reached eventually at
which "ignition" could be distinguished from
"slow combustion" as follows, The oven was
preheated and stabilized at the required con-
trol temperature before each experiment was
started. There was a temporary disturbance to
the oven temperature when the block was put
in and connected up to the recording system.
For the purposes of a comparative study of
combustible fluids, especially where evidence
for the "ignition" of one, but a failure of
"ignition" of the other, under identical control
conditions was sought, experiments were often
performed simultaneously on two impregnated
blocks. Prior to each experiment the insulation
block was impregnated uniformly with the same
amount of one or other of the alcohols (10
cm 3) by dissolving it in diethyl ether (50 cm 3)
543
and allowing this solution to penetrate the
block. The ether was then evaporated off in a
low-temperature drying over (< 325 K) over a
period of 2 h.
In order to monitor the internal combustion
behaviour, a pair of linked thermocouples was
inserted through a hole drilled between the
centers of two opposite faces of the insulation
block, so that one junction was located at the
center of the cube and the other several cen-
timeters external to the surface. Thus a mea-
sure of the temperature difference between
the center of the cube and the (constant) oven
temperature could be recorded as a function of
time. The distinction between stable, exother-
mic reaction and fully developed ignition (un-
stable reaction) could be clearly discerned from
these temperature-time records. The mini-
mum spontaneous ignition temperature was
determined as the mean value of the lowest
unstable temperature and the highest stable
temperature.
The ultimate precision with which the
changeover temperature, termed the water-
shed temperature, was "bracketed" was gov-
erned by the limit of the temperature control
of the oven over long periods (+ 1 K). But it
was also influenced by the number of experi-
ments performed on a particular fluid in the
vicinity of the watershed oven temperature. In
practice, the spontaneous ignition temperature
could be determined with confidence to the
highest precision when six or more experimen-
tal results were obtained showing either
marginally stable or marginally unstable behav-
ior.
Experimental Results
The temperature-time records displayed in Fig.
1 represent "back-to-back" experiments involv-
ing l-octanol and 1-decanol. Initially there is a
negative displacement of the thermocouple sig-
nal, which is associated with the rapid attain-
ment of the oven temperature of the external
junction relative to the cold internal junction.
The rate of increase of the measured tempera-
ture difference from its minimum towards the
internally uniform state is governed by the
thermal conductivity of the insulation material
and the rate of volatilization of fluid from the
544 A. C. MCINTOSH ET AL.

A B

201
40 40

nCsHlsOH

ZERO . . . .

nCloH21OH
ZERO--

r ; r . . . . . .
0 1 2 3 4 2 3 4
t/hrs t/hrs
Fig. 1. Simultaneous A T - t i m e records obtained during the exothermic oxidation of
n-octanol and n-decanol within a 5-cm cube of porous insulation material. The
displacement of one recorder pen from the other is given by the small offset at the start
of each signal. A. Unstable reaction of both alcohols at 7" = 443 + 1 K. B. Unstable
reaction of n-decanol but near stable reaction of n-octanol at T~ = 441 _+ 1 K.

block. As has been shown in the context of the
spontaneous ignition of cellulosic materials, the
inflexion in the signal that occurs during this
heating period is associated with the evapora-
tion and loss of volatile fluid [5]. This initial
stage lasted about 2 h under the conditions
adopted in this series of experiments. There
then follows a period of a slowly increasing
internal temperature, which is associated with
exothermic oxidation within the insulation.
Both of the alcohols undergo "ignition" in the
result shown in Fig. la, as is manifest by the
extremely high temperature excess (AT > 300
K) measured during the unstable reaction at
an oven temperature of 443 + l K. By con-
trast, at an oven temperature of 441 + 1 K,
"ignition" of 1-decanol is still detected, but the
exothermic reaction of 1-octanol remains sta-
ble (Fig. lb). The maximum temperature rise
measured in the latter was less than 50 K.
Thus not only is the distinction clear between
ignition and nonignition in these pairs of re-
sults, but also the behavior of two alcohols at
identical conditions is readily distinguished.
The overall ignition delay, including the heat-
ing time, exceeded 6 h at conditions close to
unstable behavior. The time-to-ignition of the
lower molecular mass alcohol was the shorter
of the two. The reasons for this time difference
are not yet clear.
All the alcohols reached ignition in the tests
discussed here. Moreover it was not possible to
establish a clear distinction between the mini-
mum ignition temperature of the Cg-C~t alco-
hols, which may be connected with their rela-
tively low volatility at the watershed oven tem-
perature (Table 1 and Fig. 2). However, a quite
strong dependence of watershed temperature on
volatility emerged for the alcohols of lower
boiling point (C9H19OH-C6HI3OH). We may
speculate that there would be no possibility of
ignition of alcohols of lower molecular mass
within the insulation under the present test
conditions. Although this could be tested ex-
perimentally, a controlling effect of the evapo-
ration process may not be so obvious because
there is the additional possibility that also the
reactivity with respect to the autoxidation is
AUTOIGNITION OF FLUIDS IN INSULATION MATERIALS 545

TABLE I To gain some understanding of this phe-

Minimum Ignition Temperatures and Boiling Points of the nomenon, we consider a theoretical approach
n-Alcohols under the Test Conditions using a spatially uniform form of the governing
Fuel T~ (K) B.Pt. (K) equations, which ignores diffusive effects. Such
an approach is justified in the early stages of
1-CllH23OH 429 + 2 515.5 the self-heating, since generally there is enough
1-CI()I-t21OH 433 + 1 504
1-CgH]9OH 433 4- 2 488 oxygen available within the pore structure for
I-CsHI7OH 442 4- 1 468 its supply by diffusion not to be a rate-control-
I-C7HI~OH 444 + 2 444 ling step.
1-C~HI3OH 455 + 2 430 Thus diffusion and the volatile (i.e., gas-
phase) oxidation reaction are neglected in or-
der to focus attention on the competitive ef-
reduced as the carbon chain length becomes fects of the reactive term of the dispersed
shorter, just as the n-alkanes show a markedly liquid (which decreases slowly due to the loss
diminished reactivity at C < 6. of liquid reactant) and the evaporative heat
loss.
SIMPLIFIED MATHEMATICAL MODEL Neglecting the depletion of oxygen, one can
write the equations of conservation of energy
One of the purposes of this paper is to estab- and the combustible fluid (ignoring re-con-
lish a more fundamental understanding of the densation) as follows:
autoignition of combustible fluids in porous
Energy
media, i.e., an understanding that does not rely
so much on the empiricism that this subject ¢ ! dT'
has so far received. It is found that the classi- p, Cp, dt'
cal approach to criticality is not sufficient for Oxidation
this phenomenon since there can be situations h'S'
where, even though a stable final steady state ×A'e -e'/R'r'- V---T(T'- T~)
is predicted, the transient temperature behav- tteat transfer
ior before this is to all intents and purposes at surface
indicating strong ignition behavior. (1)

1031z-J'l"
1.8 2.0 2.2 2.4 2.6 2.8 3.0
, t J : ~ t 12 Evaporadon
C,o ~ ca c7
Combustible fluid
10 i " C8 C9 C~o

dt' Evaporation
-P"I l
#.al ~" Oxidation
8 ~.
×A'e E'/R'T', (2)
where standard notation is used for enthalpy
(AH'), temperature (T'), activation energy
t
(E'), density (p'), specific heat (cp), surface
area (S'), and volume (V'). The subscripts 0 2
and L refer to oxygen and the combustible
300 350 4;0 450 500 liquid, respectively, and all dashed quantities
¥/K
are dimensional. The remaining terms repre-
Fig. 2. Dependence of vapor pressure of the n-alcohols on
sent heat transfer coefficient (h'), reaction fre-
temperature (solid lines, left hand and lower axis). The
linear relationship of l n ( p ' / p ' a) versus 1 / T ' is also shown quencies (A',F'), ambient temperature (T')
(broken lines, right hand upper axis). The gradient is and the temperature coefficient for evapora-
proportional to the enthalpy of vaporization. tion (7",i).
546 A . C . MCINTOSH ET AL.

For the purposes of nondimensionalization, At first sight these equations might appear to
we construct a temperature variable along the be a simple modification of the classical
lines of Gray and Wake [8, 9] which has the Semenov equations for the heating up of a
advantage of keeping ambient temperature as (dry) reactive pile [12], that is the classical
a distinguished parameter in the subsequent criticality problem with greater stability from
analysis. Concerning the evaporative terms, we the heat sink due to evaporation (3rd term in
follow a similar procedure to that used in the energy equation). However the presence of
earlier work concerning the influence of water x (the slowly reducing) combustible liquid con-
vapor in reactive systems [10,11]. Thus we centration in the first term alters the picture
write: substantially such that a crucial value of con-
Temperature centration (dependent on the other parameters
R' T' t' in the problem) becomes the all-determining
u---; Timet= (3a,3b) factor in the subsequent thermal behavior of
E' p~CpsV'/S'h' the system.
Preexponential terms
A' Ft THE EXISTENCE OF A TEMPERATURE-
•
CONCENTRATION WATERSHED CURVE
A - S I h /! p s cl pI~ V I ~ F S'h'/p'scpsV"
It is obvious from Eqs. 8 and 9 that the final
(4a, 4b)
stationary state with d x / d t = d u / d t = 0 is
Ratio of evaporation simply the trivial solution x = 0; u = u a. Thus
temperature coefficient to undoubtedly at long times, there is always just
one stable point in the u - x phase plane.
activation temperature
Indeed strictly one has lost criticality (accord-
T" ing to the classical definition) in that there is
Be -~- E ' / R " (5) no longer an unstable stationary state along
the middle branch of the classical S-shaped
Heat of reaction
u - ua diagram [9].
Q - R'A H°xid " (6a) Thus there is no doubt that in the end the
t l l
cpsE l¥oxid final steady state is always simply the total loss
of fluid with the material at ambient tempera-
Latent heat of evaporation
ture. However, the temperature histories re-
veal that large increases in temperature can
Qc- C'psE---~L ~Ps]-7, (6b) take place for small changes in starting condi-
tions, thus indicating that for some situations
Mass fraction of combustible liquid
the steady state will not in reality be achieved.
X ~-- pta , (7)
For all practical purposes one has ignition.
Consider an initial concentration of com-
The densities p', and p~ are a reference liquid bustible liquid x0: Since dx/dtlo < 0 (always),
density and the bulk density of the porous we have two scenarios depending on whether
material respectively• The equations then be- d u / d t l o < 0 or d u / d t l o > 0:
come
du / dtlo < 0
Energy
du In this case, it then follows (since dx/dtlo < O)
d----t = Q A x e - 1 / " - (u - ua) - QcFxe -~e/u. that d u / d x l o > 0 and thus u will constantly
reduce with time until u = u a is reached.
(8)
Combustible Liquid du / dtlo > 0
dx
-- = -Fxe ,e/u _ Axe-1/u. (9) In this case with dx/dtlo < O, we have du/dx[o
dt < O, so that as x reduces, u increases with
A U T O I G N I T I O N O F F L U I D S IN I N S U L A T I O N M A T E R I A L S 547

time and will continue to do so until d u / d x = 0 ever as soon as u0 is above this curve then the
at some later time (i.e., until some point on the temperature history is very different. In this
d u / d x = 0 locus is reached). Thus one can see latter case (see for example the starting condi-
that the du/dxlo = 0 locus is an important tion x 0 = 0.444, label ( ~ in Fig. 3), the tem-
condition and from Eq. 8 is given by perature rises sharply with x (combustible liq-
(Uo - Ua) uid concentration) reducing more quickly, until
(10) another point on the d u / d x = 0 locus is
x° = ( ( Q A ) e 1/. _ ( Q e F ) e - ~ / , , )
reached. After this, theoretically there is a final
with an asymptote given by reduction to u = u,, but obviously in a practi-
cal case, the large temperature increase will in
(1 - f i e )
fact lead to ignition. In Fig. 4 the locus of
In( A---~)
(11) du/dxlo = 0 is plotted for three values of fie,
u~ QA
the ratio of activation energies. The first case
/3e = 0.1 gives an asymptote u~ = 0.145 ( > u,
In Fig. 3 the locus of du/dxlo = 0 is plotted = 0.11), but the other two cases yield us val-
(dotted) from Eq. 10 for (QA) = 100, (Q~F) = ues below u a (u~ = 0.108 for /3e = 0.33 and
0.2 and u a = 0.11. Thus the dominant reaction u~ = 0.080 for /3e = 0.5). Thus for the higher
is considered to be the oxidation of the com- fie values, the character of the locus alters
bustible fluid with a small but significant heat with a maximum x 0 occurring, beyond which
exchange from the evaporation reaction. The no solution for du/dxlo = 0 can be found.
lower part of the curve we term an "attractor" Phase plane plots can be obtained from the
line, since there is a convergence of the tran- other/3 e curves marked in Fig. 4 (i.e., /3e = 0.1
sient solution to this line (see unbroken curves),
as long as u 0 is below the upper branch of the Initial
curve (termed as the "watershed" line). How- Temperaturs uo

Initial uo
Temperature
0.60

0.40
QAgl00, QcF'0.2, ua=0.11
'i
0.300.4:I"00"50
! QA=100, QcF=0.2, u,=0.1t
0.30 ~ ~ =0.1, 0.33, 0.5

i
~ ~,,=0.33, A=I, F=I \
0.20

I - " - ---- ~,=0.1

~ ',Watershed / '
0.10
F[F.
t ~ -~
~,--o.s
. . . . . .
-- - Watershed
A~mctor
-- = =~.--o.33
i - - "- ¢,=0.1
I ~,.~A ~ - 0 , 4 4 4 Watershed
0.10 ~ ....... ~ 7 U o_=_0 . _ 143 . . . . --- -- ----~------'--'------ = p.=0.33
L . . . . J , , , i . . . . i . . . . i
0.00 0.25 0.50 0,75 1.00
Initial combustible concentration x0
Fig. 4. Loci of du/dxlo = 0 in u 0 - x 0 p l a n e for ( Q A ) =
0.00 0.25 0.5 0.75 1.0 100, (QcF)= 0.2, u a = 0.11. Plots are s h o w n for t h r e e

InitialConcentratiXo
on
Fig. 3. Uo-Xo p h a s e plots showing m a r k e d c h a n g e in ther-
mal r e s p o n s e a b o v e a n d b e l o w the w a t e r s h e d line. The
t i m e plots are for x 0 = 0.444, with u 0 = 0.143 (below the
w a t e r s h e d line) and u 0 = 0.149 ( a b o v e the w a t e r s h e d line).
u , = 0.11, (QA) = 100, (Q~F) = 0.2, A = 1, F = 1, /3e =
0.33.
v a l u e s of /3e (ratio of e v a p o r a t i o n t e m p e r a t u r e coefficient
to a c t i v a t i o n t e m p e r a t u r e ) . F o r any fie, the b o t t o m part of
the curve is the a t t r a c t o r (stable) line w h i c h will lead to the
slow c o n v e r g e n c e to the final s t e a d y s t a t e (u o = 0.11). T h e
top part of the curve is the w a t e r s h e d ( u n s t a b l e ) line such
that u 0 > t/watershe
d l e a d s to large i n c r e a s e s in t e m p e r a t u r e
until a r e d u c e d c o n c e n t r a t i o n is r e a c h e d and a final decay
invoked.
548 A. C. MCINTOSH ET AL.

and /3~ = 0.5). The time histories will again be Initial

markedly different above the watershed line. It T M n p e l l l l U l ~ U0

is of further interest to note that beyond the 0.60

tip of the locus for each fie in Fig. 4, that any

x 0 starting condition in this region leads to a QcF:20

large temperature rise such that for all practi- 0.40

cal purposes no stability will be achieved. QA,,100,/~' "0.33, u,"0.11

The watershed temperature is thus seen to
0.30 QJ " 0 . 0 2 , 0.2, 2.0, 20.0
depend on the ratio fie of evaporation temper-
ature coefficient to activation temperature. For
fixed values of the other parameters, the re- 0.20
duction of ]~e slowly increases the watershed - Q©F=2

temperature. It is important to recognize that QcF__..O.~-L: "- - Watershed

: :_-- -: . OoF:O2
the watershed temperature for this phe- 0.10
----_i " A.~,c,o~ ___Oo,:2
nomenon is not linked with a new (unstable) - - . . . . . . QcF=20
stationary state. The only final stationary state
, . . . . . r ,
is u = u a (all at ambient temperature), but 0.00
~ , i

0.25 0.50
. . . .

0.75
i . . . .

large temperature maxima take place if the
initial temperature is above a well-defined
threshold, which has been shown to depend
crucially on the amount of combustible liquid
in the porous material and its volatility.
DISCUSSION
The watershed curves that are obtained from
different Q~ F values are shown in Fig. 5. These
have a particular relevance to the experiments
reported here since the change of Qc F effec-
tively measures the changing volatility of the
fluid. Insofar that the ratio of vapor pressure
to ambient pressure (p'/p',) of a liquid satisfies
d(ln(p'/p' a)) - A H~
d(1/T') R'
where AH~ is the enthalpy of vaporization
(Fig. 2), this leads to the evaporation term of
Eqs. 1 and 2 being of the form F'e-v"/r' with
the implication that the evaporation tempera-
ture coefficient T" is the same as AH'UR'.
For a particular class of compounds the en-
thalpy of vaporization is constant, and is 60 + 3
kJ mo1-1 for the n-alcohols (Fig. 2). If an
overall activation energy for the low-tempera-
ture oxidation of 150-200 kJ mol 1 is as-
sumed, then the ratio /3e would be about 0.33
for the n-alcohols, and would be approximately
constant throughout the class. This value for
/3e is used in the data used to construct Fig. 5
and the volatility change is thus represented by
1.00
Initial c o m b u s t i b l e ~ xo
Fig. 5. The effect of volatility F on the loci of du/dxlo = 0
in the Uo-Xo plane for (QA) = 100, /3e = 0.33, u , = 0.11.
Plots are shown for four values of (QcF) (which for
constant latent heat Qc is directly proportional to volatil-
ity). These curves show the trend found experimentally,
that increasing the volatility ( F ) tends to increase the
watershed temperature. Thus the less volatile combustible
fluids are more likely to cause self-heating in the porous
medium.
the change in F. The variation of the constant
term associated with the graph of ln(p'/p',) vs.
1 / T ' over the range 1-C6H13OH to 1-
CltH23OH is consistent with a 10-fold varia-
tion in the computed values of F.
It is evident that an increase in volatility
raises the watershed temperature so that as
found in the experiments, the less volatile
combustible fluids are more likely to cause
self-heating in the porous medium, since as
can be seen from Fig. 5, the watershed temper-
ature is lower. The change in behavior brought
about by the variation of /3e (Fig. 4) demon-
strates the qualitative distinctions that can arise
as fluids of similar volatility but different
chemical reactivity undergo autoignition in
porous insulation materials.
REFERENCES
1. Bowes, P. C., Self-heating: Evaluating and Controlling
the Hazard, HMSO, 1984.
2. Britton, L. G., 23rd Annual Symposium on Loss Pre-
vention, AIChe, paper 92c, 1990.
A U T O I G N I T I O N OF FLUIDS IN I N S U L A T I O N M A T E R I A L S
3. Lindner, H., and Seibring, H., Chimie-lng. Tech.
39:667 (1967).
4. Boddington, T., Griffiths, J. F., and Hasegawa, K.,
Combust. Flame 55:297 (1984).
5. Griffiths, J. F., Hasko, S. M., and Tong, A. W.,
Combust. Flame 59:1 (1985).
6. Griffiths, J. F., and Kordylewski, W., Twenty-Fourth
Symposium (International) on Combustion, The Com-
bustion Institute, Pittsburgh, 1992, p. 1777.
7. Gray, B. F., Merkin, J. H., and Griffiths, J. F.,
Twenty-Fourth Symposium (International) on Combus-
tion, The Combustion Institute, Pittsburgh, 1992, p.
1775.
COMMENTS
Carlos Fernandez-PeUo, University of California,
Berkeley, USA. Your conclusion that ignition
occurs due to a reaction in the liquid phase is
based on the observation that ignition occurs
at a temperature below the boiling point of the
fuel. Depending on the partial pressure at the
liquid's surface, a liquid can evaporate at a
temperature well below its boiling point. Thus,
this is not a reason to eliminate a gas phase
reaction. Furthermore, your analysis and con-
clusions would be the same if the liquid phase
reaction is replaced with a gas phase reaction,
which makes most physical sense.
Author's Reply. Our reply is that (as with the
comment below from Dr. Stephen Niksa), al-
though gas phase oxidation may affect the de-
tails of the behavior of the system, it is unlikely
that this is the controlling factor. There is
some evidence, particularly with regard to the
long induction times involved, that there is
condensed phase oxidation taking place. Fur-
ther work is being done to seek to expose more
clearly the chemistry involved.
Stephen Niksa, SRI International, USA. Your
inference of liquid-phase combustion is incon-
sistent with (a) the presence of fuel vapor
throughout the pore volume at temperatures
well below the boiling point and (b) the faster
oxidation rates of fuel vapors compared to the
burning rates of condensed fuels. Considering
that the volume of vapor released up to the
ignition point is far larger than the pore vol-
549
8. Gray, B. F., and Wake, G. C., Combust. Flame, 71:101
(1988).
9. Gray, B. F., Proc. R. Soc. Lond. A4 29:449-458
(1990).
10. McIntosh, A. C., Proceedings of the Joint Meeting of
the British and German Sections of the Combustion
Institute, Cambridge, 1993, pp. 327-330.
11. McIntosh, A. C., IMA J. Appl. Math. 51(3):217 238
(1993).
12. McIntosh, A. C., and Tolputt, T. A., Combust. Sci.
Technol. 69:133-145 (1990).
Received 18 April 1994; revised 18 May 1994
ume of the insulation, can the diffusion of 0 2
be governing the observed induction times?
Author's Reply. It seems unlikely that the oxi-
dation of fuel vapor is the controlling factor in
these phenomena. We believe that it is a con-
densed phase oxidation (which may be as ad-
sorbed species or some other similar state).
This is the important distinction in our analyti-
cal model. Thus, the exothermic reaction is
certainly dependent on some fuel concentra-
tion.
We agree that displacement of oxygen oc-
curs during the evaporative stage. However,
the time to the temperature maximum (subcrit-
ical or supercritical) is often many hours (thus
rather longer than the one hour or so for bulk
evaporation) and sufficiently long for oxygen to
diffuse back into the porous medium. It is
important for us to put these processes on a
quantitative basis with a spatially distributed
model.
A. Kanury, Oregon State University, USA. Can
you tell me where in your model are the appar-
ently important variables--the porosity of the
insulation, the ambient O 2 content, insulation
thickness--taken into account?
Author's Reply. As yet the model does not take
account of porosity, 0 2 content, etc. These
features are part of a distributed model which
we plan to develop at a later stage in the
project.
550
Lawrence A. Kennedy, The Ohio State Univer-
sity, USA. The phenomenon you describe is not
unknown in the literature. Our own work on
combustion in porous media (this symp, 04E-2)
shows that a thermal field can couple with low
reaction and so feed back energy, drastically
elevating the temperature and resulting in a
reaction wave propagating through the porous
media. There is a wealth of work under the
title of filtration combustion which is in the
literature and which is relevant to the problem
you are examining. I'd suggest that you draw
upon this existing knowledge.
Author's Reply. Our initial interest is in the
origin of, and conditions for, the onset of a
high temperature combustion phenomenon. In
the next stage we would wish to understand
better the nature of the propagating combus-
tion wave, which could be clearly seen in the
experiments under supercritical conditions.
Your indication of the source of information
about related phenomena is helpful to that
part of our program.
Patrick J. Pagni, University of California, Berke-
ley, USA. Bowes, in your ref. 1, p. 394, suggests
that for linseed oil on cotton an optimum fuel
loading for self-heating occurs at one-half, i.e.,
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A. C. MCINTOSH ET AL.
the weight of the absorbed combustible fluid
equals the dry weight of the insulating mate-
rial. Does your analysis confirm this observa-
tion and permit determination of the optima
for other fuels and substrates? Experimentally,
you've made a valuable contribution showing
that an inert substrate readily supports self-
heating. Why didn't you make a standard
"Beever plot" of critical conditions as a func-
tion of size for your system [1]?
REFERENCE
Beever, P. F., in S.F.P.E. Handbook of Fire Protection
Engineering, P. J. DiNenno, et al., eds., NFPA, Quincy,
MA, 1988, pp. 1-341-1-359.
Author's Reply. After preliminary experimental
tests, we made the present study at only one
specific loading throughout, in order to unify
the tests across the range of alcohols used. We
recognize that the amount of combustible fluid
initially present could well be important (as
shown by Bowes) and we plan to investigate
this. Similarly we worked only with one size of
block of inert material in the experiments. The
simple, non-spatially-dependent theory does
not take account directly of size. Beever plots
can be made once we alter block sizes in future
experiments.